U.S. patent number 7,528,091 [Application Number 11/822,012] was granted by the patent office on 2009-05-05 for magnesium-containing carrier component and application to olefin polymerization.
This patent grant is currently assigned to Mitsui Chemicals, Inc.. Invention is credited to Hideki Bando, Terunori Fujita, Makoto Mitani, Yasushi Nakayama, Yoshiho Sonobe.
United States Patent |
7,528,091 |
Nakayama , et al. |
May 5, 2009 |
Magnesium-containing carrier component and application to olefin
polymerization
Abstract
Solid fine particles which contain a magnesium atom, an aluminum
atom and a C.sub.1-20 alkoxy group simultaneously, are insoluble in
a hydrocarbon solvent, and have an average particle diameter of 3
to 80 .mu.m, and an olefin polymerization catalyst containing the
solid fine particles and a transition metal compound in the groups
3 to 11 in the periodic table, exhibit a very high olefin
polymerization activity without combination with an expensive
organoaluminum oxy compound or organoboron compound and maintains a
high activity in polymerization for a long time, and an olefin
polymer excellent in powdery properties can be produced by using
the olefin polymerization catalyst. The transition metal compound
in the groups 3 to 11 in the periodic table includes a transition
metal compound having a ligand containing two or more atoms
selected from a boron atom, a nitrogen atom, an oxygen atom, a
phosphorus atom and a sulfur atom.
Inventors: |
Nakayama; Yasushi (Sodegaura,
JP), Bando; Hideki (Sodegaura, JP), Sonobe;
Yoshiho (Sodegaura, JP), Mitani; Makoto
(Sodegaura, JP), Fujita; Terunori (Sodegaura,
JP) |
Assignee: |
Mitsui Chemicals, Inc. (Tokyo,
JP)
|
Family
ID: |
32179086 |
Appl.
No.: |
11/822,012 |
Filed: |
June 29, 2007 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20080015401 A1 |
Jan 17, 2008 |
|
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
10526906 |
Oct 13, 2005 |
7253132 |
|
|
|
Foreign Application Priority Data
|
|
|
|
|
Oct 23, 2002 [JP] |
|
|
2002-308352 |
Sep 12, 2003 [JP] |
|
|
2003-320805 |
|
Current U.S.
Class: |
502/115; 502/103;
526/124.2; 526/124.9; 526/161 |
Current CPC
Class: |
C08F
10/00 (20130101); C08F 4/64048 (20130101); C08F
10/00 (20130101); C08F 110/02 (20130101); C08F
110/02 (20130101); C08F 4/022 (20130101); C08F
110/02 (20130101); C08F 2500/17 (20130101); C08F
2500/18 (20130101); C08F 2500/04 (20130101); C08F
110/02 (20130101); C08F 2500/17 (20130101); C08F
2500/18 (20130101); C08F 2500/03 (20130101) |
Current International
Class: |
C08F
4/02 (20060101); C08F 4/602 (20060101) |
Field of
Search: |
;502/103,115
;526/124.2,124.9,161 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
4250285 |
February 1981 |
Kashiwa et al. |
4542199 |
September 1985 |
Kaminsky et al. |
4814313 |
March 1989 |
Murata et al. |
5091353 |
February 1992 |
Kioka et al. |
5623033 |
April 1997 |
Kioka et al. |
|
Foreign Patent Documents
|
|
|
|
|
|
|
0 069 951 |
|
Jan 1983 |
|
EP |
|
0 273 695 |
|
Jul 1988 |
|
EP |
|
0 358 264 |
|
Mar 1990 |
|
EP |
|
0 435 514 |
|
Jul 1991 |
|
EP |
|
58-19309 |
|
Feb 1983 |
|
JP |
|
4-211405 |
|
Aug 1992 |
|
JP |
|
7-330821 |
|
Dec 1995 |
|
JP |
|
10-279618 |
|
Oct 1998 |
|
JP |
|
2000-191718 |
|
Jul 2000 |
|
JP |
|
Primary Examiner: Lu; Caixia
Attorney, Agent or Firm: Birch, Stewart, Kolasch &
Birch, LLP
Parent Case Text
This application is a Divisional of application Ser. No. 10/526,906
filed on Oct.13, 2005 ,now U.S. Pat. No. 7,253,132 and for which
priority is claimed under 35 U.S.C. .sctn. 120; and this
application claims priority of Application Nos. 2002-308352 and
2003-320805 filed in Japan on Oct. 23, 2002 and Sep. 12, 2003 under
35 U.S.C. .sctn. 119; the entire contents of all are hereby
incorporated by reference.
Claims
What is claimed is:
1. An olefin polymerization catalyst comprising a carrier component
suitable as an olefin polymerization catalyst, which is insoluble
in a hydrocarbon solvent, is in the form of a solid fine particles
having an average particle diameter of 3 to 80 .mu.m, and contains
a magnesium atom, an aluminum atom and a C.sub.1-20 alkoxy group
simultaneously, wherein the molar ratio of magnesium atom to
aluminum atom (Mg/Al) is in the range of 40 to 150, and the molar
ratio of alkoxy group to aluminum atom (alkoxy group/Al) is in the
range of 0.2 to 2.0.
2. An olefin polymerization catalyst comprising: (A) a transition
metal compound from any one of groups 3 to 11 in the periodic
table, having a ligand containing two or more atoms selected from a
boron atom, a nitrogen atom, an oxygen atom, a phosphorous atom and
a sulfur atom, (B) a carrier component suitable as an olefin
polymerization catalyst, which is insoluble in a hydrocarbon
solvent, is in the form of a solid fine particles having an average
particle diameter of 3 to 80 .mu.m, and contains a magnesium atom,
an aluminum atom and a C.sub.1-20 alkoxy group simultaneously,
wherein the molar ratio of magnesium atom to aluminum atom (Mg/Al)
is in the range of 1.0 to 300, and the molar ratio of alkoxy group
to aluminum atom (alkoxy group/Al) is in the range of 0.05 to 2.0,
and (C) a specific organometallic compound, if necessary.
3. The olefin polymerization catalyst according to claim 2, wherein
the transition metal compound (A) is carried on the carrier
component (B).
4. The olefin polymerization catalyst according to claim 2, wherein
the molar ratio of magnesium atom to aluminum atom (Mg/Al) is in
the range of 40 to 150, and the molar ratio of alkoxy group to
aluminum atom (alkoxy group/Al) is in the range of 0.2 to 2.0.
5. The olefin polymerization catalyst according to claim 2, which
is obtained by contacting a magnesium halide with a C.sub.1-20
alcohol and then contacting the product with an organoaluminum
compound represented by the general formula (Z) AlR.sub.nX.sub.3-n
(Z) wherein R represents a C.sub.1-20 hydrocarbon group, X
represents a halogen atom or a hydrogen atom, n is an integer of 1
to 3, and when there are a plurality of Rs, Rs may be the same or
different, and when there are a plurality of Xs, Xs may be the same
or different.
Description
TECHNICAL FIELD
The present invention relates to an olefin polymerization catalyst
and a process for producing an olefin polymer by using the olefin
polymerization catalyst and in particular to an olefin
polymerization catalyst not containing an organoaluminum oxy
compound or an organoboron compound used conventionally as an
olefin polymerization catalyst component, a process for producing
an olefin polymer by using the olefin polymerization catalyst, and
polyolefins excellent in powdery properties obtained by this
process.
BACKGROUND ART
There is known a method of polymerizing an olefin wherein a
metallocene compound having a group having conjugated .pi.
electrons particularly cyclopentadiene and its derivative as a
ligand is used as a catalyst to be combined with an organoaluminum
oxy compound or an organoboron compound. For example, JP-A 58-19309
discloses a method of polymerizing an olefin wherein
bicyclopentadienyl zirconium dichloride and methyl aluminoxane are
used as a catalyst. Recently, a system wherein olefin
polymerization proceeds without using combination with an
organoaluminum oxy compound or an organoboron compound is also
disclosed. For example, JP-A 4-211405 discloses a method of
polymerizing an olefin by using a combination of a zirconium
metallocene compound and a solid carrier obtained by contacting
magnesium chloride and an active hydrogen-free electron donor with
active hydrogen-containing electron donor. Further, JP-A 7-330821
discloses a method of polymerizing an olefin by using a combination
of a titanium metallocene compound and a solid component obtained
by reacting a magnesium compound such as magnesium halide with an
organoaluminum compound.
However, a majority of known methods including the method of JP-A
58-19309 suffer from a problem that the metallocene compound when
used without combination with an expensive organoaluminum oxy
compound or organoboron compound cannot exhibit a high olefin
polymerization activity. Even if the metallocene compound exhibits
a high olefin polymerization activity by combination with an
expensive organoaluminum oxy compound or organoboron compound, the
duration of the activity was often short. Further, the bulk density
of a formed polymer after polymerization is low to make handling
difficult, and when such catalysts are applied to a gaseous phase
or liquid phase polymerization method, the resulting polymer
adheres to a polymerizer wall thus deteriorating heat transfer to
make cooling difficult and to permit formation of polymer
agglomerates, and thus there are many problems to be solved in
process in order to use such catalysts in producing polyolefin in
an industrial scale.
In recently disclosed methods of permitting olefin polymerization
to proceed without combination with an organoaluminum oxy compound
or an organoboron compound, on one hand, there still remain many
features to be improved from an economical point of view and from
the viewpoint of large-scale production. In JP-A 4-211405 supra,
for example, dibutyl magnesium which is expensive and unstable in
the air should be used as a starting material in order to regulate
the particle diameter of magnesium chloride as a carrier, and in
JP-A 7-330821 supra, expensive and unstable diethoxy magnesium is
used as a carrier. It is hardly said that these known techniques
not using combination with an organoaluminum oxy compound or an
organoboron compound are satisfactory in respect of the
polymerization activity, the powdery properties of a formed
polymer, and molecular weight characteristics such as
molecular-weight distribution etc.
DISCLOSURE OF INVENTION
The present invention was made in view of the technical background
described above, and the object of the present invention is to
provide a polymerization catalyst exhibiting a high olefin
polymerization activity without combination with an expensive
organoaluminum oxy compound or organoboron compound and maintaining
a high activity in polymerization for a long time, as well as a
process for producing olefin polymers excellent in powdery
properties by using the catalyst. This object is achieved by using
an olefin polymerization catalyst containing solid fine particles
prepared by a specific method, which contain a magnesium atom, an
aluminum atom and a C.sub.1-20 alkoxy group simultaneously, satisfy
the requirements (i) the molar ratio of magnesium atom to aluminum
atom (Mg/Al) is in the range of 1.0<(Mg/Al).ltoreq.300.0, (ii)
the molar ratio of alkoxy group to aluminum atom (OR/Al) is in the
range of 0.5<(OR/Al)<2.0, and (iii) the average particle
diameter is in the range of 3 to 80 .mu.m, and are insoluble in a
hydrocarbon solvent.
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention relates to 1) a carrier component containing
magnesium, 2) an olefin polymerization catalyst containing the
carrier component, 3) a method of polymerizing an olefin by using
the olefin polymerization catalyst, and 4) polyolefin obtained by
this polymerization method. Hereinafter, the means to solve the
problem in each item is described in detail.
Carrier Component Containing Magnesium
The carrier component containing magnesium in the present invention
(hereinafter abbreviated sometimes to "carrier") is characterized
by containing a magnesium atom, an aluminum atom and a C.sub.1-20
alkoxy group simultaneously, being insoluble in a hydrocarbon
solvent, and having an average particle diameter of 3 to 80 .mu.m.
The molar ratio of magnesium atom to aluminum atom (Mg/Al) in the
carrier component is in the range of 1.0<Mg/Al.ltoreq.300.0, and
the molar ratio of alkoxy group to aluminum atom (OR/Al) is
0.05<OR/Al<2.0.
The phrase "being insoluble in a hydrocarbon solvent" means that a
soluble part of magnesium atoms is 0.5 weight % or less under
stirring in at least one solvent selected from hexane, decane and
toluene for 1 minute to 1 hour under atmospheric pressure in the
temperature range of 0.degree. C. to the inherent boiling point of
the solvent, and also that soluble parts of aluminum atoms and
alkoxy groups are each 1 weight % or less under stirring in at
least one solvent selected from hexane, decane and toluene for 1
minute to 1 hour under atmospheric pressure at room
temperature.
The carrier component of the present invention may contain other
metal atoms and other organic groups than magnesium, aluminum and
an alkoxy group, but is preferably free of a transition metal atom
in the group 4, such as titanium, zirconium and hafnium. For
example, when a titanium atom is contained in the carrier component
of the present invention, an olefin polymer derived from compound
(A) described later, that is, a transition metal compound in the
groups 3 to 11 in the periodic table, having a ligand containing
two or more atoms selected from a boron atom, a nitrogen atom, an
oxygen atom, a phosphorus atom and a sulfur atom, and an olefin
polymer derived from a titanium atom contained therein, are
simultaneously formed, and thus the primary structure of the
resulting polymer is hardly controlled. For the reason described
above, it is preferable that the carrier component of the present
invention is free of a transition metal atom in the group 4 and
simultaneously does substantially not exhibit an olefin
polymerization activity in combination with optionally used
component (C) described later.
The total amount of a magnesium atom, an aluminum atom and a
C.sub.1-20 alkoxy group contained in the carrier component of the
present invention is usually in the range of 10 to 90 weight %,
preferably in the range of 15 to 60 weight %, particularly
preferably 20 to 40 weight %, from the viewpoint of the polyolefin
polymerization activity of a carrier component-containing
polymerization catalyst described later and the powdery properties
of polyolefin obtained as a result of polymerization. The largest
component other than the magnesium atom, aluminum atom and
C.sub.1-20 alkoxy group contained in the carrier component is a
halogen atom. When the halogen atom is a chlorine atom, the amount
of chlorine atom in the carrier component ranges from about 20
weight % at the minimum to about 80 weight % at the maximum. In
addition, an alcohol corresponding to the C.sub.1-20 alkoxy group
or a remaining organic solvent etc. used at the time of preparing
the carrier component may be contained in the carrier
component.
The C.sub.1-20 alkoxy group in the carrier component of the present
invention is a group derived from a C.sub.1-20 alcohol used as a
starting component at the time of preparing the carrier component
as described later. The C.sub.1-20 alkoxy group includes a methoxy
group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy
group, i-butoxy group, t-butoxy group, n-pentoxy group, i-amyloxy
group, n-hexoxy group, n-heptoxy group, 2-ethylhexoxy group,
n-octoxy group, dodecoxy group, octadecyloxy group, oleyloxy group,
benzyloxy group, phenylethoxy group, cumyloxy group,
i-propylbenzyloxy group etc., a halogen-containing alkoxy group
such as trichloromethoxy group, trichloroethoxy group,
trichlorohexoxy group etc., and a lower alkyl-containing phenoxy
group such as phenoxy group, cresoxy group, ethylphenoxy group,
nonylphenoxy group, cumylphenoxy group, naphthoxy group etc., among
which a methoxy group, ethoxy group, propoxy group, butoxy group,
pentoxy group, i-amyloxy group, hexoxy group, heptoxy group,
2-ethylhexoxy group, octoxy group, dodecoxy group etc. are
preferable.
The molar ratio of magnesium atom to aluminum atom (Mg/Al) in the
carrier component of the present invention is usually in the range
of 1.0<Mg/Al.ltoreq.300.0, preferably
30.0<Mg/Al.ltoreq.250.0, more preferably
30.0<Mg/Al.ltoreq.200.0, still more preferably
35.0<Mg/Al.ltoreq.200.0, further more preferably
40.0<Mg/Al.ltoreq.150.0, from the viewpoint of olefin
polymerization activity and the powdery properties of formed
polyolefin. The molar ratio of alkoxy group to aluminum atom
(OR/Al) is usually in the range of 0.05<OR/Al<2.0, preferably
0.1.ltoreq.OR/Al<1.8, more preferably 0.2<OR/Al<1.0, in
further increasing the olefin polymerization activity.
When the carrier component of the present invention having an
average particle diameter of 3 to 80 .mu.m, preferably 3 to 50
.mu.m, is used as an olefin polymerization catalyst described
later, the polymerization activity is improved while the bulk
density of formed polyolefin can be increased. In the carrier
component of the present invention, a parameter which is important
similarly to the parameter of average particle diameter is
crystallite size determined by X-ray diffraction analysis of
magnesium halide constituting the carrier component. This
crystallite size is highly correlated with the polymerization
activity, and a carrier component having a small crystallite size
is considered necessary to achieve a high polymerization activity.
However, when the crystallite size is extremely small, the
polymerization activity is high, but deterioration of the particle
morphology of the catalyst component is estimated. Accordingly, the
crystallite size in the present invention is usually 3 to 80
(.ANG.), preferably 10 to 75 (.ANG.), more preferably 12 to 70
(.ANG.), still more preferably 15 to 60 (.ANG.), further more
preferably 20 to 55 (.ANG.).
The carrier component of the present invention is obtained by
contacting a magnesium halide with a C.sub.1-20 alcohol
(hereinafter, this contact is referred to sometimes as "first
contact") and then contacting the product with an organo aluminum
compound represented by the following general formula (Z)
(A1RnX3-n) (hereinafter, this contact is referred to sometimes as
"second contact"), but the method of preparing the carrier
component of the present invention is not limited to this
preparation method.
As the magnesium halide, magnesium chloride and magnesium bromide
are preferably used. As the magnesium halide, a commercial product
may be used as it is, or the magnesium halide may be prepared
separately from alkyl magnesium and the magnesium halide thus
prepared can also be used without isolation.
The C.sub.1-20 alcohol includes alcohols corresponding to the
above-mentioned C.sub.1-20 alkoxy groups, and examples thereof
include methanol, ethanol, n-propanol, i-propanol, n-butanol,
i-butanol, t-butanol, n-pentanol, i-amyl alcohol, n-hexanol,
n-heptanol, 2-ethyl hexanol, n-octanol, dodecanol, octadecyl
alcohol, oleyl alcohol, benzyl alcohol, phenyl ethanol, cumyl
alcohol, i-propylbenzyl alcohol etc., a halogen-containing alcohol
such as trichloromethanol, trichloroethanol, trichlorohexanol etc.,
and phenol or lower alkyl-containing phenol such as cresol, ethyl
phenol, nonyl phenol, cumyl phenol, naphthol etc., among which
methanol, ethanol, propanol, butanol, pentanol, i-amyl alcohol,
hexanol, heptanol, 2-ethyl hexanol, octanol and dodecanol are
preferable.
The magnesium halide may be contacted with the C.sub.1-20 alcohol
in the presence of a solvent. The solvent includes aliphatic
hydrocarbons such as hexane, heptane, octane, decane, dodecane and
kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane,
methylcyclopentane etc.; aromatic hydrocarbons such as benzene,
toluene, xylene etc.; halogenated hydrocarbons such as ethylene
dichloride, chlorobenzene, dichloromethane etc., or mixtures
thereof.
Contact is carried out usually under heating. In heating, a
temperature up to the boiling point of the solvent used can be
arbitrarily selected. The contact time is varied depending on
contact temperature, and for example, under conditions where
n-decane is used as solvent and the heating temperature is
130.degree. C., there appears a phenomenon where the reaction
mixture is made uniform by contact for about 4 hours, which is
indicative of completion of contact. Contact is carried out usually
by using a unit facilitating contact under stirring etc. When the
contact is initiated, the system is usually heterogeneous, but as
the contact proceeds, the reaction mixture is made gradually
uniform and finally liquefied. Regardless of the degree of
liquefaction, the carrier component of the present invention is
useful as a component of the olefin polymerization catalyst, but is
prepared preferably via a process involving complete liquefaction,
from the viewpoint of the olefin polymerization activity and the
powdery properties of the formed polyolefin.
The thus prepared contact product of the magnesium halide and
C.sub.1-20 alcohol (hereinafter referred to sometimes as "first
contact product) may be used without distilling the solvent away or
after removal of the solvent etc. used at the time of contact.
Usually, the product is subjected to the subsequent step without
distilling the solvent away.
The first contact product obtained by the above method is then
contacted (=second contact) with an organoaluminum compound
represented by the following general formula (Z):
A1R.sub.nX.sub.3-n (Z)
In the general formula (Z), R represents a C.sub.1-20 hydrocarbon
group, specifically a methyl group, ethyl group, propyl group,
butyl group, hexyl group, octyl group and decyl group. X represents
a halogen atom such as a chlorine atom, bromine atom etc. or a
hydrogen atom. n is an integer of 1 to 3, preferably 2 or 3. When
there are a plurality of Rs, the Rs may be the same or different,
and when there are a plurality of Xs, the Xs may be the same or
different. Specifically, the following compounds are used as the
organoaluminum compound. The organoaluminum compound meeting such
requirements includes trialkyl aluminum such as trimethyl aluminum,
triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum,
trioctyl aluminum, tri-2-ethylhexyl aluminum etc.; alkenyl aluminum
such as isoprenyl aluminum etc.; dialkylaluminum halide such as
dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl
aluminum chloride, diisobutyl aluminum chloride, dimethyl aluminum
bromide etc.; alkyl aluminum sesquihalide such as methyl aluminum
sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum
sesquichloride, butyl aluminum sesquichloride, ethyl aluminum
sesquibromide etc.; alkyl aluminum dihalide such as methyl aluminum
dichloride, ethyl aluminum dichloride, isopropyl aluminum
dichloride, ethyl aluminum dibromide etc.; and alkyl aluminum
hydride such as diethyl aluminum hydride, diisobutyl aluminum
hydride etc., among which trimethyl aluminum, triethyl aluminum,
triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, diethyl
aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum
dichloride and diisobutyl aluminum hydride are preferable.
The contact method for the second contact is not particularly
limited, but usually the second contact is carried out by a method
of adding the organoaluminum compound represented by the general
formula (Z) to the first contact product under stirring. In this
step, the first contact product may have been diluted with a
solvent, and as the solvent, a hydrocarbon not having active
hydrogen can be used without particular limitation, but usually the
second contact can be carried out efficiently by using, as the
solvent in the second contact, the solvent used in the first
contact without distilling it away. The organoaluminum compound
added to the first contact product may be used after dilution with
a solvent, or may be added without dilution with a solvent, but
usually the organoaluminum compound is used in a form diluted with
an aliphatic saturated hydrocarbon such as n-decane and n-hexane or
an aromatic hydrocarbon solvent such as toluene and xylene. When
the organoaluminum compound is added, the compound is added to the
first contact product usually over 5 minutes to 5 hours. When
cooling performance in the catalytic system is sufficient, it can
be added for a short time, and when the performance is
insufficient, it is added preferably for a long time. The
organoaluminum compound may be added all at once or several times
in divided portions. When added in divided portions, the
organoaluminum compounds in divided portions may be the same or
different, and the temperature of the first contact product upon
divided addition may be the same or different.
The organoaluminum compound represented by the general formula (Z)
is used such that the molar ratio of the organoaluminum compound in
the second contact to the magnesium atom in the first contact
product is usually 0.1 to 50, preferably 0.5 to 30, more preferably
1.0 to 20, still more preferably 1.5 to 15, further still more
preferably 2.0 to 10.
In the method of preparing the carrier by the second contact, a
particularly preferable mode of the second contact is described
below.
In contacting the first contact product with the organoaluminum
compound represented by the general formula (Z) above, it is
preferable that, for example, a hydrocarbon dilution of the
magnesium compound is contacted with a hydrocarbon dilution of the
organoaluminum compound so that both the dilutions are reacted.
Usually, the molar ratio of the organoaluminum compound to the
magnesium compound is varied depending on its type and contact
conditions, but is preferably 2 to 10. The shape and size of the
solid product is varied depending on its forming conditions. To
obtain a solid product having a regulated shape and particle
diameter, it is preferably to avoid rapid formation, and for
example, when the magnesium compound and the organoaluminum
compound, both in a liquid form, are contacted and mixed with each
other to form a solid product by mutual reaction, it is preferable
that the two are contacted and mixed at a low temperature so as to
prevent rapid formation of solids, followed by increasing the
temperature to form a solid product gradually. According to this
method, it is easy to regulate the particle diameter of the solid
product, and a granular or spherical solid product having a narrow
particle size distribution can be easily obtained.
A polymer obtained by slurry polymerization or gaseous phase
polymerization using the thus obtained granular or spherical
carrier component excellent in particle size distribution is
granular or spherical, has narrow particle-size distribution and
high bulk density, and is excellent in flowability.
The carrier component described above is not only useful as a
constitutional component of the olefin polymerization catalyst
described later but is also utilizable as a catalyst for many
organic synthesis reactions by virtue of the functions of Lewis
acid contained in the carrier component.
Olefin Polymerization Catalyst Containing the Carrier Component
The olefin polymerization catalyst of the present invention
contains the carrier component described above. The polymerization
catalyst includes an olefin polymerization catalyst comprising: (A)
a transition metal compound in the groups 3 to 11, having a ligand
containing two or more atoms selected from a boron atom, a nitrogen
atom, an oxygen atom, a phosphorus atom and a sulfur atom, (B) the
carrier component described above, and if necessary (C) a specific
organometallic compound.
The transition metal compound (A) in the groups 3 to 11, having a
ligand containing two or more atoms selected from a boron atom, a
nitrogen atom, an oxygen atom, a phosphorus atom and a sulfur atom
may be carried (and is carried more preferably from the viewpoint
of the powdery properties of a formed olefin polymer) on the
carrier component (B).
The transition metal compound (A) in the groups 3 to 11, having a
ligand containing two or more atoms selected from a boron atom, a
nitrogen atom, an oxygen atom, a phosphorus atom and a sulfur atom,
used in the present invention, includes for example compounds (a-1)
to (a-27) described below. These transition metal compounds may be
used alone or as a mixture of two or more thereof.
Compound (a-1)
As the component (A) in the present invention, compound (a-1)
represented by the following general formulae (I) to (III) can be
used.
##STR00001## wherein N . . . M.sup.1, N . . . M.sup.2 and N . . .
M.sup.3 generally show that the two elements are coordinated, but
in the present invention, they may or may not be coordinated.
M.sup.1 in formula (I), M.sup.2 in formula (II) and M.sup.3 in
formula (II) may be the same or different and each represent a
transition metal atom selected from the groups 3 to 11 in the
periodic table (the group 3 also containing lanthanoids),
preferably a transition metal atom in the groups 3 to 6 and 8 to
10, more preferably a transition metal atom in the group 4, 5 or 6,
still more preferably a metal atom in the group 4 or 5. Examples
thereof include scandium, titanium, zirconium, hafnium, vanadium,
niobium, tantalum, cobalt, rhodium, yttrium, chromium, molybdenum,
tungsten, manganese, rhenium, iron, ruthenium, nickel, palladium
etc., preferably scandium, titanium, zirconium, hafnium, vanadium,
niobium, tantalum, iron, cobalt, rhodium, nickel, palladium etc.,
more preferably titanium, zirconium, hafnium, vanadium, niobium,
tantalum, chromium, molybdenum etc., still more preferably
titanium, zirconium, hafnium, vanadium, niobium, tantalum etc.
m in formula (I), m' in formula (II) and m'' in formula (III) may
be the same or different and each represent an integer of 1 to 6,
preferably an integer of 1 to 4, more preferably an integer of 1 to
3, still more preferably an integer of 1 to 2.
k in formula (I), k' in formula (II) and k'' in formula (III) may
be the same or different and each represent an integer of 1 to 6,
preferably an integer of 1 to 4, more preferably an integer of 1 to
3, still more preferably an integer of 1 to 2.
In formula (I), A represents an oxygen atom, a sulfur atom or a
substituent --R.sup.6-containing nitrogen atom (--N(R.sup.6)--),
preferably an oxygen atom or a nitrogen atom.
In formula (I), D represents a nitrogen atom, a phosphorus atom or
a substituent --R.sup.7-containing carbon atom, preferably
substituent --R.sup.7-containing carbon atom.
In formula (I), R.sup.1 to R.sup.7 may be the same or different and
each represent a hydrogen atom, a halogen atom, a hydrocarbon
group, an oxygen-containing group, a nitrogen-containing group, a
boron-containing group, a sulfur-containing group, a
phosphorus-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group, and two or more of these groups may be bound
to one another to form a ring.
In formula (II), G represents an oxygen atom, a sulfur atom or a
substituent --R.sup.12-containing nitrogen atom (--N(R.sup.12)--),
preferably an oxygen atom.
In formula (II), E represents N-binding --R.sup.13 and --R.sup.14,
or .dbd.C(R.sup.15)R.sup.16.
In formula (II), R.sup.8 to R.sup.16 may be the same or different
and each represent a hydrogen atom, a halogen atom, a hydrocarbon
group, an oxygen-containing group, a nitrogen-containing group, a
boron-containing group, a sulfur-containing group, a
phosphorus-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group, and two or more of these groups may be bound
to one another to form a ring.
In formula (III), J represents a nitrogen atom, a phosphorus atom
or a substituent --R.sup.18-containing carbon atom
(--C(R.sup.18).dbd.), preferably a substituent
--R.sup.18-containing carbon atom.
In formula (III), T represents a nitrogen atom or a phosphorus
atom, preferably a nitrogen atom.
In formula (III), L represents a nitrogen atom, a phosphorus atom
or a substituent --R.sup.19-containing carbon atom
(--C(R.sup.19).dbd.), preferably a substituent
--R.sup.19-containing carbon atom.
In formula (III), Q represents a nitrogen atom, a phosphorus atom
or a substituent --R.sup.20-containing carbon atom
(--C(R.sup.20).dbd.) preferably a substituent --R.sup.20-containing
carbon atom.
In formula (III), R represents a nitrogen atom, a phosphorus atom
or a substituent --R.sup.21-containing carbon atom
(--C(R.sup.21).dbd.), preferably a substituent
--R.sup.21-containing carbon atom.
In formula (III), R.sup.17 to R.sup.21 may be the same or different
and each represent a hydrogen atom, a halogen atom, a hydrocarbon
group, an oxygen-containing group, a nitrogen-containing group, a
boron-containing group, a sulfur-containing group, a
phosphorus-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group, and two or more of these groups may be bound
to one another to form a ring.
When m in formula (I) is 2 or more, R.sup.1s, R.sup.2, R.sup.3s,
R.sup.4s, R.sup.5s, R.sup.6s or R.sup.7s may be the same or
different. When m is 2 or more, two groups out of the groups
represented by R.sup.1 to R.sup.7 may be bound to each other.
When m' in formula (II) is 2 or more, R.sup.8s, R.sup.9s,
R.sup.10s, R.sup.11s, R.sup.12s, R.sup.13s, R.sup.14s, R.sup.15s or
R.sup.16s may be the same or different. When p is 2 or more, two
groups out of the groups represented by R.sup.8 to R.sup.16 may be
bound to each other.
When m'' in formula (III) is 2 or more, R.sup.17s, R.sup.18s,
R.sup.19s, R.sup.20s or R.sup.21s may be the same or different.
When r is 2 or more, two groups out of the groups represented by
R.sup.17 to R.sup.21 may be bound to each other.
The halogen atom represented by R.sup.1 to R.sup.7 in formula (I),
R.sup.8 to R.sup.16 in formula (II) and R.sup.17 to R.sup.21 in
formula (III) includes fluorine, chlorine, bromine and iodine.
Specific examples of the hydrocarbon group represented by R.sup.1
to R.sup.7 in formula (I), R.sup.8 to R.sup.16 in formula (II) and
R.sup.17 to R.sup.21 in formula (III) include a C.sub.1-30,
preferably C.sub.1-20, linear or branched alkyl group such as
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, neopentyl, n-hexyl etc.;
a C.sub.2-30, preferably C.sub.2-20, linear or branched alkenyl
group such as vinyl, allyl, isopropenyl etc.;
a C.sub.2-30, preferably C.sub.2-20, linear or branched alkynyl
group such as ethynyl, propargyl etc.;
a C.sub.3-30, preferably C.sub.3-20, saturated cyclic hydrocarbon
group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
adamanthyl etc.;
a C.sub.5-30 unsaturated cyclic hydrocarbon group such as
cyclopentadienyl, indenyl, fluorenyl etc.;
a C.sub.6-30, preferably C.sub.6-20, aryl group such as phenyl,
benzyl, naphthyl, biphenylyl, terphenylyl, phenanthryl, anthryl
etc.; and
an alkyl-substituted aryl group such as methylphenyl,
isopropylphenyl, t-butylphenyl, dimethylphenyl, diisopropylphenyl,
di-t-butylphenyl, trimethylphenyl, triisopropylphenyl,
tri-t-butylphenyl etc.
The hydrocarbon group may be the one whose hydrogen atom is
replaced by a halogen, and examples thereof include a C.sub.1-30,
preferably C.sub.1-20, halogenated hydrocarbon group such as
trifluoromethyl, pentafluorophenyl, chlorophenyl etc.
The hydrocarbon group may be substituted with other hydrocarbon
groups, and examples thereof include an alkyl group substituted
with an aryl group such as benzyl, cumyl etc.
The hydrocarbon group may be substituted with a heterocyclic
compound residue; an oxygen-containing group such as an alkoxy
group, aryloxy group, ester group, ether group, acyl group,
carboxyl group, carbonate group, hydroxy group, peroxy group,
carboxylic anhydride group etc.; a nitrogen-containing group such
as an amino group, imino group, amide group, imido group, hydrazino
group, hydrazono group, nitro group, nitroso group, cyano group,
isocyano group, cyanate group, amidino group, diazo group, a group
whose amino group is converted into an ammonium salt, etc.; a
boron-containing group such as a borane diyl group, borane triyl
group, diboranyl group etc.; a sulfur-containing group such as a
mercapto group, thioester group, dithioester group, alkylthio
group, arylthio group, thioacyl group, thioether group, thiocyanate
group, isothiocyanate group, sulfone ester group, sulfonamide
group, thiocarboxyl group, dithiocarboxyl group, sulfo group,
sulfonyl group, sulfinyl group, sulphenyl group etc.; a
phosphorus-containing group such as a phosphide group, phosphoryl
group, thiophosphoryl group, phosphate group etc.; and a
silicon-containing group, a germanium-containing group or a
tin-containing group.
As described above, the hydrocarbon group may be substituted with
an oxygen-containing group, a nitrogen-containing group, a
boron-containing group, a sulfur-containing group, a
phosphorus-containing group, a silicon-containing group, a
germanium-containing group, a tin-containing group etc., and in
this case, it is desired that an atomic group characterizing a
substituent group such as an oxygen-containing group does not bind
directly to a carbon atom in N or D in formula (I), a carbon atom
in E in formula (II), and a carbon atom in J, L, Q, T or R in
formula (III).
Particularly preferable among these are a C.sub.1-30, preferably
C.sub.1-20, linear or branched alkyl group such as methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl,
neopentyl, n-hexyl etc.; a C.sub.6-30, preferably C.sub.6-20, aryl
group such as phenyl, naphthyl, biphenylyl, terphenylyl,
phenanthryl, anthryl etc.; and a substituted aryl group substituted
with 1 to 5 substituent atoms or groups such as a halogen atom, a
C.sub.1-30, preferably C.sub.1-20, alkyl group or alkoxy group, a
C.sub.6-30, preferably C.sub.6-20, aryl group or aryloxy group.
Two or more groups of R.sup.1 to R.sup.7, preferably adjacent
groups, may be bound to each other to form a ring; two or more
groups of R.sup.8 to R.sup.16, preferably adjacent groups, may be
bound to each other to form a ring; two or more groups of R.sup.17
to R.sup.21, preferably adjacent groups, may be bound to each other
to form a ring. The ring includes, for example, condensed-ring
groups such as a benzene ring, naphthalene ring, acenaphthene ring,
indene ring etc., wherein a hydrogen atom on the condensed ring may
be replaced by an alkyl group such as methyl, ethyl, propyl or
butyl.
The oxygen-containing group represented by R.sup.1 to R.sup.7 in
formula (I), R.sup.8 to R.sup.16 in formula (II) and R.sup.17 to
R.sup.21 in formula (III) is a group containing 1 to 5 oxygen
atoms, and does not include a heterocyclic compound residue
described later. The oxygen-containing group does not include a
group containing a nitrogen atom, a sulfur atom, a phosphorus atom,
a halogen atom or a silicon atom having an oxygen atom bound
directly thereto. Examples of the oxygen-containing group include,
for example, an alkoxy group, aryloxy group, ester group, ether
group, acyl group, carboxyl group, carbonate group, hydroxy group,
peroxy group, carboxylic anhydride group etc., among which an
alkoxy group, aryloxy group, acetoxy group, carbonyl group, hydroxy
group etc. are preferable. When the oxygen-containing group
contains carbon atoms, it is desired that the number of carbon
atoms is in the range of 1 to 30, preferably 1 to 20.
The nitrogen-containing group represented by R.sup.1 to R.sup.7 in
formula (I), R.sup.8 to R.sup.16 in formula (II) and R.sup.17 to
R.sup.21 in formula (III) is a group containing 1 to 5 nitrogen
atoms, and does not include a heterocyclic compound residue
described later. Examples of the nitrogen-containing group include,
for example, an amino group, imino group, amide group, imido group,
hydrazino group, hydrazono group, nitro group, nitroso group, cyano
group, isocyano group, cyanate group, amidino group, diazo group, a
group whose amino group is converted into an ammonium salt, etc.,
preferably an amino group, imino group, amide group, imido group,
nitro group, cyano group etc. When the nitrogen-containing group
contains carbon atoms, it is desired that the number of carbon
atoms is 1 to 30, preferably 1 to 20.
The boron-containing group represented by R.sup.1 to R.sup.7 in
formula (I), R.sup.8 to R.sup.16 in formula (II) and R.sup.17 to
R.sup.21 in formula (III) is a group containing 1 to 5 boron atoms,
and does not include a heterocyclic compound residue described
later. Examples of the boron-containing group include, for example,
boron-containing groups such as a borane diyl group, borane triyl
group, diboranyl group etc., preferably a boryl group substituted
with one or two of C.sub.1-30, preferably C.sub.1-20, hydrocarbon
groups or a borate group substituted with one to three of the
hydrocarbon groups. When the group is substituted with two or more
hydrocarbon groups, the hydrocarbon groups may be the same or
different.
The sulfur-containing group represented by R.sup.1 to R.sup.7 in
formula (I), R.sup.8 to R.sup.16 in formula (II) and R.sup.17 to
R.sup.21 in formula (III) is a group containing 1 to 5 sulfur
atoms, and does not include a heterocyclic compound residue
described later. Examples of the sulfur-containing group include,
for example, a mercapto group, thioester group, dithioester group,
alkylthio group, arylthio group, thioacyl group, thioether group,
thiocyanate group, isothiocyanate group, sulfone ester group,
sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo
group, sulfonyl group, sulfinyl group, sulphenyl group, sulfonate
group and sulfinate group, among which a sulfonate group, sulfinate
group, alkylthio group and arylthio group are preferable. When the
sulfur-containing group contains carbon groups, it is desired that
the number of carbon atoms is in the range of 1 to 30, preferably 1
to 20.
The phosphorus-containing group represented by R.sup.1 to R.sup.7
in formula (I), R.sup.8 to R.sup.16 in formula (II) and R.sup.17 to
R.sup.21 in formula (III) is a group containing 1 to 5 phosphorus
atoms, and does not include a heterocyclic compound residue
described later. Examples of the phosphorus-containing group
include, for example, a phosphino group, phosphoryl group,
phosphothioyl group, phosphono group etc.
The heterocyclic compound residue represented by R.sup.1 to R.sup.7
in formula (I), R.sup.8 to R.sup.16 in formula (II) and R.sup.17 to
R.sup.21 in formula (III) is a cyclic group containing 1 to 5
heteroatoms, and the heteroatom includes O, N, S, P and B. The
cycle includes, for example, a 4- to 7-membered monocycle and
multi-cycle, preferably a 5- to 6-membered monocycle and
multi-cycle. Specifically, mention is made of for example a
nitrogen-containing compound residue such as pyrrole, pyridine,
pyrimidine, quinoline, triazine etc.; an oxygen-containing compound
residue such as furan, pyran etc.; and a sulfur-containing compound
residue such as thiophene etc., and these groups may be further
substituted with a substituent group such as a C.sub.1-30,
preferably C.sub.1-20, alkyl group or a C.sub.1-30, preferably
C.sub.1-20, alkoxy group.
The silicon-containing group represented by R.sup.1 to R.sup.7 in
formula (I), R.sup.8 to R.sup.16 in formula (II) and R.sup.17 to
R.sup.21 in formula (III) is a group containing 1 to 5 silicon
atoms, and examples thereof include a silyl group such as a
hydrocarbon-substituted silyl group and a siloxy group such as a
hydrocarbon-substituted siloxy group. Specific examples include
methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl,
diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl,
dimethylphenylsilyl, dimethyl-t-butylsilyl,
dimethyl(pentafluorophenyl)silyl etc. Among these, methylsilyl,
dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl,
triethylsilyl, dimethylphenylsilyl, triphenylsilyl etc. are
preferable, and trimethylsilyl, triethylsilyl, triphenylsilyl,
dimethylphenylsilyl etc. are particularly preferable. The
hydrocarbon-substituted siloxy group is specifically
trimethylsiloxy etc. When the silicon-containing group contains
carbon atoms, it is desired that the number of carbon atoms is in
the range of 1 to 30, preferably 1 to 20.
The germanium-containing group and tin-containing group represented
by R.sup.1 to R.sup.7 in formula (I), R.sup.8 to R.sup.16 in
formula (II) and R.sup.17 to R.sup.21 in formula (III) include
groups wherein in the silicon-containing group, silicon is replaced
by germanium or tin.
Examples of R.sup.1 to R.sup.7 in formula (I), R.sup.8 to R.sup.16
in formula (II) and R.sup.17 to R.sup.21 in formula (III) described
above are described in more detail.
Preferable examples of the oxygen-containing group include an
alkoxy group such as methoxy, ethoxy, n-propoxy, isopropoxy,
n-butoxy, isobutoxy, tert-butoxy etc., an aryloxy group such as
phenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy etc., an acyl
group such as formyl, acetyl, benzoyl, p-chlorobenzoyl,
p-methoxybenzoyl etc., and an ester group such as acetyloxy,
benzoyloxy, methoxycarbonyl, phenoxycarbonyl,
p-chlorophenoxycarbonyl etc.
Preferable examples of the nitrogen-containing group include an
alkylamino group such as methylamino, dimethylamino, diethylamino,
dipropylamino, dibutylamino, dicyclohexylamino etc., an arylamino
group or alkylarylamino group such as phenylamino, diphenylamino,
ditolylamino, dinaphthylamino, methylphenylamino etc., an imino
group such as methylimino, ethylimino, propylimino, butylimino,
phenylimino etc., an amide group such as acetamide,
N-methylacetamide, N-methylbenzamide etc., and an imido group such
as acetimido, benzimido etc.
Preferable examples of the sulfur-containing group include an
alkylthio group such as methylthio, ethylthio etc., an arylthio
group such as phenylthio, methylphenylthio, naphthylthio etc., a
thioester group such as acetylthio, benzoylthio,
methylthiocarbonyl, phenylthiocarbonyl etc., a sulfone ester group
such as methyl sulfonate, ethyl sulfonate, phenyl sulfonate etc.,
and a sulfonamide group such as phenylsulfonamide,
N-methylsulfonamide, N-methyl-p-toluenesulfonamide etc.
The sulfonate group includes methyl sulfonate, trifluoromethane
sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate,
trimethyl benzene sulfonate, triisobutyl benzene sulfonate,
p-chlorobenzene sulfonate, pentafluorobenzene sulfonate etc., and
the sulfinate group includes methyl sulfinate, phenyl sulfinate,
benzyl sulfinate, p-toluene sulfinate, trimethyl benzene sulfinate,
pentafluorobenzene sulfinate etc.
The phosphorus-containing group includes a phosphino group such as
dimethyl phosphino, diphenyl phosphino etc., a phosphoryl group
such as methyl phosphoryl, isopropylphosphoryl, phenylphosphoryl
etc., a phosphothioyl group such as methylphosphothioyl,
isopropylphosphothioyl, phenylphosphothioyl etc., a phosphono group
for example a phosphate group and a phosphoric acid group such as
dimethyl phosphate, diisopropyl phosphate, diphenyl phosphate
etc.
In formula (I), n is a number satisfying the valence of M.sup.1,
and is specifically an integer of 0 to 5, preferably 0 to 4, more
preferably 0 to 3.
In formula (II), q is a number satisfying the valence of M.sup.2,
and is specifically an integer of 0 to 5, preferably 0 to 4, more
preferably 0 to 3.
In formula (III), r is a number satisfying the valence of M.sup.3,
and is specifically an integer of 0 to 5, preferably 0 to 4, more
preferably 0 to 3.
When X.sup.1 in formula (I) is an atom or a group other than oxygen
atom, n is preferably an integer of 1 to 4, more preferably 1 to
3.
When X.sup.2 in formula (II) is an atom or a group other than
oxygen atom, q is preferably an integer of 1 to 4, more preferably
1 to 3.
When X.sup.3 in formula (III) is an atom or a group other than
oxygen atom, r is preferably an integer of 1 to 4, more preferably
1 to 3.
In formula (I), X.sup.1 represents an atom or a group selected
arbitrarily from a hydrogen atom, a halogen atom, an oxygen atom, a
hydrocarbon group, an oxygen-containing group, a
nitrogen-containing group, a boron-containing group, a
sulfur-containing group, a phosphorus-containing group, a
halogen-containing group, a heterocyclic compound residue, a
silicon-containing group, an aluminum-containing group, a
germanium-containing group and a tin-containing group.
In formula (II), X.sup.2 represents an atom or a group selected
arbitrarily from a hydrogen atom, a halogen atom, an oxygen atom, a
hydrocarbon group, an oxygen-containing group, a
nitrogen-containing group, a boron-containing group, a
sulfur-containing group, a phosphorus-containing group, a
halogen-containing group, a heterocyclic compound residue, a
silicon-containing group, an aluminum-containing group, a
germanium-containing group and a tin-containing group.
In formula (III), X.sup.3 represents an atom or a group selected
arbitrarily from a hydrogen atom, a halogen atom, an oxygen atom, a
hydrocarbon group, an oxygen-containing group, a
nitrogen-containing group, a boron-containing group, a
sulfur-containing group, a phosphorus-containing group, a
halogen-containing group, a heterocyclic compound residue, a
silicon-containing group, an aluminum-containing group, a
germanium-containing group and a tin-containing group.
When n in formula (I) is 2 or more, a plurality of groups
represented by X.sup.1 may be the same or different; when n in
formula (II) is 2 or more, a plurality of groups represented by
X.sup.2 may be the same or different; and when n in formula (III)
is 2 or more, a plurality of groups represented by X.sup.3 may be
the same or different.
When n in formula (I) is 2 or more, a plurality of groups
represented by X.sup.1 may be bound to one another to form a ring;
when n in formula (II) is 2 or more, a plurality of groups
represented by X.sup.2may be bound to one another to form a ring;
and when n in formula (III) is 2 or more, a plurality of groups
represented by X.sup.3 may be bound to one another to form a
ring.
The halogen atom represented by X.sup.1 in formula (I), X.sup.2 in
formula (II) and X.sup.3 in formula (III) includes fluorine,
chlorine, bromine and iodine.
The hydrocarbon group represented by X.sup.1 in formula (I),
X.sup.2 in formula (II) and X.sup.3 in formula (III) includes the
same groups as illustrated for R.sup.1 to R.sup.7 in formula (I).
Examples thereof include an alkyl group such as methyl, ethyl,
propyl, butyl, hexyl, octyl, nonyl, dodecyl, eicosyl etc.; a
C.sub.3-30 cycloalkyl group such as cyclopentyl, cyclohexyl,
norbornyl, adamantyl etc.; an alkenyl group such as vinyl,
propenyl, cyclohexenyl etc.; an arylalkyl group such as benzyl,
phenylethyl, phenylpropyl etc.; and an aryl group such as phenyl,
tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl,
biphenylyl, naphthyl, methylnaphthyl, anthryl, phenanthryl etc. The
hydrocarbon group includes a halogenated hydrocarbon, specifically
a C.sub.1-20 hydrocarbon group wherein at least one hydrogen atom
is replaced by a halogen. Among these, the C.sub.1-20 hydrocarbon
group is preferable.
The oxygen-containing group represented by X.sup.1 in formula (I),
X.sup.2 in formula (II) and X.sup.3 in formula (III) includes the
same groups as illustrated for R.sup.1 to R.sup.21 described above,
and examples thereof include a hydroxy group; an alkoxy group such
as methoxy, ethoxy, propoxy, butoxy etc.; an aryloxy group such as
phenoxy, methylphenoxy, dimethylphenoxy, naphthoxy etc.; an
arylalkoxy group such as phenylmethoxy, phenylethoxy etc.; an
acetoxy group; a carbonyl group etc.
The nitrogen-containing group represented by X.sup.1 in formula
(I), X.sup.2 in formula (II) and X.sup.3 in formula (III) includes
the same groups as illustrated for R.sup.1 to R.sup.21 described
above, and examples thereof include an amino group; an alkylamino
group such as methylamino, dimethylamino, diethylamino,
dipropylamino, dibutylamino, dicyclohexylamino etc; and an
arylamino group or an alkylarylamino group such as phenylamino,
diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino
etc.
Specifically, the boron-containing group represented by X.sup.1 in
formula (I), X.sup.2 in formula (II) and X.sup.3 in formula (III)
includes BR.sub.4 wherein R is hydrogen, an alkyl group, an
optionally substituted aryl group, a halogen atom etc.
The sulfur-containing group represented by X.sup.1 in formula (I),
X.sup.2 in formula (II) and X.sup.3 in formula (III) includes the
same groups as illustrated for R.sup.1 to R.sup.21 described above,
and examples thereof include a sulfonate group such as methyl
sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl
sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate,
triisobutylbenzene sulfonate, p-chlorobenzene sulfonate,
pentafluorobenzene sulfonate etc.; a sulfinate group such as methyl
sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluene sulfinate,
trimethylbenzene sulfinate, pentafluorobenzene sulfinate etc.; an
alkylthio group; and an arylthio group.
The phosphorus-containing group represented by X.sup.1 in formula
(I), X.sup.2 in formula (II) and X.sup.3 in formula (III) includes,
for example, a trialkylphosphine group such as trimethylphosphine,
tributylphosphine, tricyclohexylphosphine etc.; a triarylphosphine
group such as triphenylphosphine, tritolylphosphine etc.; a
phosphite group (phosphide group) such as methylphosphite,
ethylphosphite, phenylphosphite etc.; a phosphonic acid group; and
a phosphinic acid group.
Specifically, the halogen-containing group represented by X.sup.1
in formula (I), X.sup.2 in formula (II) and X.sup.3 in formula
(III) includes a fluorine-containing group such as PF.sub.6,
BF.sub.4 etc., a chlorine-containing group such as ClO.sub.4,
SbCl.sub.6 etc., and an iodine-containing group such as IO.sub.4
etc.
The heterocyclic compound residue represented by X.sup.1 in formula
(I), X.sup.2 in formula (II) and X.sup.3 in formula (III) includes
the same groups as illustrated for R.sup.1 to R.sup.21 described
above.
Specifically, the silicon-containing group represented by X.sup.1
in formula (I), X.sup.2 in formula (II) and X.sup.3 in formula
(III) includes the same groups as illustrated for R.sup.1 to
R.sup.21 described above, and examples thereof include a
hydrocarbon-substituted silyl group such as phenylsilyl,
diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl,
tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl,
tritolylsilyl, trinaphthylsilyl etc.; a hydrocarbon-substituted
silylether group such as trimethylsilylether; a silicon-substituted
alkyl group such as trimethylsilylmethyl etc.; and a
silicon-substituted aryl group such as trimethylsilylphenyl
etc.
Specifically, the aluminum-containing group represented by X.sup.1
in formula (I), X.sup.2 in formula (II) and X.sup.3 in formula
(III) includes AlR.sub.4 wherein R represents hydrogen, an alkyl
group, an optionally substituted aryl group, a halogen atom
etc.
Specifically, the germanium-containing group represented by X.sup.1
in formula (I), X.sup.2 in formula (II) and X.sup.3 in formula
(III) includes the same groups as illustrated for R.sup.1 to
R.sup.21 described above.
Specifically, the tin-containing group represented by X.sup.1 in
formula (I), X.sup.2 in formula (II) and X.sup.3 in formula (III)
includes the same groups as illustrated for R.sup.1 to R.sup.21
described above.
Specific examples of the transition metal compound represented by
the general formula (I), (II) or (III) above are described
below.
In the following examples, M is a transition metal atom, and
preferable examples are Sc(III), Ti(III), Ti(IV), Zr(III), Zr(IV),
Hf(IV), V(III), V(IV), V(V), Nb(V), Ta(V), Fe(II), Fe(III), Co(II),
Co(III), Rh(II), Rh(III), Rh(IV), Cr(III), Ni(II) and Pd(II). Among
these metal atoms, Ti(IV), Zr(IV), Hf(IV), V(III), V(IV), V(V),
Nb(V) and Ta(V) are preferable, and particularly Ti(IV), Zr(IV) and
Hf(IV) are preferable.
In the following examples, X represents for example a halogen such
as Cl, Br etc., an oxygen atom or an alkyl group such as methyl
etc. When there are a plurality of Xs, the Xs may be the same or
different.
n is determined by the valence of the metal M. For example, when
two monoanion species bind to the metal, n is 0 for divalent metal,
n is 1 for trivalent metal, n is 2 for tetravalent metal, and n is
3 for pentavalent metal; for example, n is 1 for a metal V(III), n
is 2 for Ti(IV), Zr(IV) or V(IV) and n is 3 for V(V); for example,
when one kind of monoanion species binds to the metal and
simultaneously one oxygen atom bind via a double bond to the metal,
n is 0 for trivalent metal, n is 1 for tetravalent metal, and n is
2 for pentavalent metal; for example, n is 0 for a metal V(III), n
is 1 for Ti(IV), Zr(IV) or V(IV), and n is 2 for V(V); for example,
when two monoanion species bind to the metal and simultaneously one
oxygen atom binds via a double bond to the metal, n is 0 for
tetravalent metal and n is 1 for pentavalent metal; for example, n
is O for a metal Ti(IV), Zr(IV) or V(IV) and n is 1 for V(V); for
example, when one kind of monoanion species binds to the metal and
simultaneously one atom binds via a single bond to the metal, n is
0 for divalent metal, n is 1 for trivalent metal, n is 2 for
tetravalent metal and n is 3 for pentavalent metal; for example, n
is 1 for a metal V(III), n is 2 for Ti(IV), Zr(IV) or V(IV), and n
is 3 for V(V).
Specific examples of the transition metal compound represented by
the general formula (I), (II) or (III) are shown below.
##STR00002## ##STR00003## ##STR00004## ##STR00005## ##STR00006##
##STR00007## ##STR00008## ##STR00009## ##STR00010## ##STR00011##
##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016##
##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021##
##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026##
##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031##
##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036##
##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041##
##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046##
##STR00047## ##STR00048## ##STR00049## ##STR00050## ##STR00051##
##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056##
##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061##
##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066##
##STR00067## ##STR00068## ##STR00069## ##STR00070## ##STR00071##
##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076##
##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081##
##STR00082## ##STR00083## ##STR00084##
In the above-illustrated compounds, .sup.tBu indicates a t-butyl
group, OMe indicates a methoxy group, Ph indicates a phenyl group,
Me indicates a methyl group, and Adm indicates an adamanthyl
group.
The transition metal compounds in the present invention can also be
exemplified by those derivatives of the above compounds wherein
zirconium was replaced by a metal selected from the groups 4 and 5
in the periodic table, such as titanium, hafnium, vanadium etc.
Compound (a-2)
As the component (A) in the present invention, compound (a-2)
represented by the following general formula (IVa) can be used.
##STR00085##
In formula (IVa), M is a transition metal atom selected from the
groups 3 to 7 in the periodic table, preferably a transition metal
atom selected from the groups 4 and 5. Specifically, M is titanium,
zirconium, hafnium, vanadium, niobium or tantalum, preferably
titanium, zirconium or vanadium.
In formula (IVa), R.sup.1 to R.sup.6 may be the same or different
and each represent a hydrogen atom, a halogen atom, a hydrocarbon
group, an oxygen-containing group, a nitrogen-containing group, a
boron-containing group, a sulfur-containing group, a
phosphorus-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group, and two or more of these groups may be bound
to each other to form a ring such as an aromatic ring, an aliphatic
ring, or a hydrocarbon ring containing a heteroatom such as a
nitrogen atom, a sulfur atom and an oxygen atom. Each of R.sup.5
and R.sup.6 is preferably a hydrocarbon group, more preferably an
aryl group substituted with an alkyl group.
The halogen atom and hydrocarbon group represented by R.sup.1 to
R.sup.6 in formula (IVa) include the same halogen atoms and
hydrocarbon groups as illustrated for R.sup.1 to R.sup.7 in the
formula (I) above.
The hydrocarbon group represented by R.sup.1 to R.sup.6 in formula
(IVa) may be substituted with an oxygen-containing group, a
nitrogen-containing group, a boron-containing group, a
sulfur-containing group, a phosphorus-containing group, a
silicon-containing group, a germanium-containing group, a
tin-containing group etc., wherein an atomic group characterizing
the substituent group such as the oxygen-containing group is
desirably not directly bound to N in formula (IVa).
The hydrocarbon group is particularly a C.sub.1-30, preferably
C.sub.1-20, linear or branched alkyl group such as methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl,
neopentyl, n-hexyl etc.; a C.sub.6-30, preferably C.sub.6-20, aryl
group such as phenyl, naphthyl, biphenylyl, terphenylyl,
phenanthryl, anthryl etc.; and a substituted aryl group substituted
with 1 to 5 substituent atoms or groups such as a halogen atom, a
C.sub.1-30, preferably C.sub.1-20, alkyl group or alkoxy group, a
C.sub.6-30, preferably C.sub.6-20, aryl group or aryloxy group.
In formula (IVa), two or more groups of R.sup.1 to R.sup.6,
preferably adjacent groups, may be bound to each other to form an
aromatic ring, an aliphatic ring, or a hydrocarbon ring containing
a nitrogen atom, a sulfur atom, an oxygen atom etc., and these
rings may further have a substituent group, and particularly
R.sup.3 and R.sup.4 are preferably bound to each other to form an
aromatic ring.
The oxygen-containing group, nitrogen-containing group,
boron-containing group, sulfur-containing group,
phosphorus-containing group, heterocyclic compound residue,
silicon-containing group, germanium-containing group and
tin-containing group represented by R.sup.1 to R.sup.6 in formula
(IVa) include the same groups as illustrated for R.sup.1 to R.sup.7
in the formula (I) above.
More specific groups of R.sup.1 to R.sup.6 in formula (IVa) include
the more specific groups illustrated as R.sup.1 to R.sup.7 in the
formula (I) above.
In formula (IVa), n is a number satisfying the valence of M, and is
specifically an integer of 1 to 5, preferably 1 to 4, more
preferably 1 to 3.
In formula (IVa), X represents a hydrogen atom, a halogen atom, a
hydrocarbon group, an oxygen-containing group, a sulfur-containing
group, a nitrogen-containing group, a boron-containing group, an
aluminum-containing group, a phosphorus-containing group, a
halogen-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group.
The halogen atom, hydrocarbon group, oxygen-containing group,
sulfur-containing group, nitrogen-containing group,
boron-containing group, aluminum-containing group,
phosphorus-containing group, halogen-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by X in formula (IVa)
include the same atoms or groups as illustrated for X.sup.1 in the
formula (I) above.
The hydrocarbon group is preferably a C.sub.1-20 group.
When n is 2 or more, a plurality of groups represented by Xs may be
the same or different, and a plurality of groups represented by Xs
may be bound to one another to form a ring.
Compound (a-2) represented by the general formula (IVa) above is
preferably a compound represented by the following general formula
(IVa'):
##STR00086##
In formula (IVa'), M is a transition metal atom selected from the
groups 4 and 5 in the periodic table, and specifically M is
titanium, zirconium, vanadium, niobium or tantalum.
In formula (IVa'), R.sup.7 to R.sup.13 may be the same or different
and each represent a hydrogen atom, a halogen atom, a hydrocarbon
group, an oxygen-containing group, a nitrogen-containing group, a
boron-containing group, a sulfur-containing group, a
phosphorus-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group, and two or more of these groups may be bound
to each other to form a ring. Each of R.sup.12 and R.sup.13 is
preferably a hydrocarbon group, more preferably an aryl group
substituted with an o-alkyl group.
The halogen atom and hydrocarbon group represented by R.sup.7 to
R.sup.13 in formula (IVa') include the same atoms and groups as
illustrated for R.sup.1 to R.sup.7 in the general formula (I)
above.
The hydrocarbon group may be substituted with an oxygen-containing
group, a nitrogen-containing group, a boron-containing group, a
sulfur-containing group, a phosphorus-containing group, a
silicon-containing group, a germanium-containing group, a
tin-containing group etc., wherein an atomic group characterizing
the substituent group such as the oxygen-containing group is
desirably not directly bound to N in formula (IVa').
The oxygen-containing group, nitrogen-containing group,
boron-containing group, sulfur-containing group,
phosphorus-containing group, heterocyclic compound residue,
silicon-containing group, germanium-containing group and
tin-containing group represented by R.sup.7 to R.sup.13 in formula
(IVa') include the same groups as illustrated for R.sup.1 to
R.sup.7 in the general formula (I) above.
More specific groups of R.sup.7 to R.sup.13 in formula (IVa')
include the more specific groups illustrated above as those of
R.sup.1 to R.sup.7 in the formula (I) above.
In formula (IVa'), n is a number satisfying the valence of M, and
is specifically an integer of 1 to 5, preferably 1 to 4, more
preferably 1 to 3.
In formula (IVa'), X represents a hydrogen atom, a halogen atom, a
hydrocarbon group, an oxygen-containing group, a sulfur-containing
group, a nitrogen-containing group, a boron-containing group, a
phosphorus-containing group, a halogen-containing group, a
heterocyclic compound residue, an aluminum-containing group, a
silicon-containing group, a germanium-containing group or a
tin-containing group.
The halogen atom, hydrocarbon group, oxygen-containing group,
sulfur-containing group, nitrogen-containing group,
boron-containing group, aluminum-containing group,
phosphorus-containing group, halogen-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by X in formula (IVa')
include the same atoms or groups as illustrated for X.sup.1 in the
formula (I) above.
When n is 2 or more, a plurality of groups represented by Xs may be
the same or different, and a plurality of groups represented by Xs
may be bound to one another to form a ring.
Specific examples of the compounds represented by the general
formula (IVa) above are shown below.
##STR00087## ##STR00088## ##STR00089## ##STR00090##
In the above-illustrated compounds, iPr indicates an isopropyl
group, tBu indicates a t-butyl group, and Ph indicates a phenyl
group.
Compound (a-3)
As the component (A) in the present invention, compound (a-3)
represented by the following general formula (IVb) can be used.
##STR00091##
In formula (IVb), M is a transition metal atom selected from the
groups 8 to 11 in the periodic table, preferably a transition metal
atom selected form the group 8 and 9. Specifically, M is iron,
ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium,
copper etc., preferably iron, ruthenium, cobalt, rhodium etc., more
preferably iron or cobalt.
In formula (IVb), R.sup.1 to R.sup.6 may be the same or different
and each represent a hydrogen atom, a halogen atom, a hydrocarbon
group, an oxygen-containing group, a nitrogen-containing group, a
boron-containing group, a sulfur-containing group, a
phosphorus-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group, and two or more of these groups may be bound
to each other to form a ring such as an aromatic ring, an aliphatic
ring, or a hydrocarbon ring containing a heteroatom such as a
nitrogen atom, a sulfur atom and an oxygen atom. Each of R.sup.5
and R.sup.6 is preferably a hydrocarbon group, more preferably an
aryl group substituted with an alkyl group.
The halogen atom and hydrocarbon group represented by R.sup.1 to
R.sup.6 in formula (IVb) include the same halogen atoms and
hydrocarbon groups as illustrated for R.sup.1 to R.sup.7 in the
formula (I) above.
The hydrocarbon group represented by R.sup.1 to R.sup.6 in formula
(IVb) may be substituted with an oxygen-containing group, a
nitrogen-containing group, a boron-containing group, a
sulfur-containing group, a phosphorus-containing group, a
silicon-containing group, a germanium-containing group, a
tin-containing group etc., wherein an atomic group characterizing
the substituent group such as the oxygen-containing group is
desirably not directly bound to N in formula (IVb).
The hydrocarbon group is particularly a C.sub.1-30, preferably
C.sub.1-20, linear or branched alkyl group such as methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl,
neopentyl, n-hexyl etc.; a C.sub.6-30, preferably C.sub.6-20, aryl
group such as phenyl, naphthyl, biphenylyl, terphenylyl,
phenanthryl, anthryl etc.; and a substituted aryl group substituted
with 1 to 5 substituent atoms or groups such as a halogen atom, a
C.sub.1-30, preferably C.sub.1-20, alkyl group or alkoxy group, a
C.sub.6-30, preferably C.sub.6-20, aryl group or aryloxy group.
In formula (IVb), two or more groups of R.sup.1 to R.sup.6,
preferably adjacent groups, may be bound to each other to form an
aromatic ring, an aliphatic ring, or a hydrocarbon ring containing
a nitrogen atom, a sulfur atom, an oxygen atom etc., and these
rings may further have a substituent group, and particularly
R.sup.3 and R.sup.4 are preferably bound to each other to form an
aromatic ring.
The oxygen-containing group, nitrogen-containing group,
boron-containing group, sulfur-containing group,
phosphorus-containing group, heterocyclic compound residue,
silicon-containing group, germanium-containing group and
tin-containing group represented by R.sup.1 to R.sup.6 in formula
(IVb) include the same groups as illustrated for R.sup.1 to R.sup.7
in the formula (I) above.
More specific groups of R.sup.1 to R.sup.6 in formula (IVb) include
the more specific groups illustrated above as those of R.sup.1 to
R.sup.7 in the formula (I) above.
In formula (IVb), n is a number satisfying the valence of M, and is
specifically an integer of 1 to 5, preferably 1 to 4, more
preferably 1 to 3.
In formula (IVb), X represents a hydrogen atom, a halogen atom, a
hydrocarbon group, an oxygen-containing group, a sulfur-containing
group, a nitrogen-containing group, a boron-containing group, an
aluminum-containing group, a phosphorus-containing group, a
halogen-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group.
The halogen atom, hydrocarbon group, oxygen-containing group,
sulfur-containing group, nitrogen-containing group,
boron-containing group, aluminum-containing group,
phosphorus-containing group, halogen-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by X in formula (IVb)
include the same atoms or groups as illustrated for X.sup.1 in the
formula (I) above.
The hydrocarbon group is preferably a C.sub.1-20 group.
When n is 2 or more, a plurality of groups represented by Xs may be
the same or different, and a plurality of groups represented by Xs
may be bound to one another to form a ring.
Compound (a-3) represented by the general formula (IVb) above is
preferably a compound represented by the following general formula
(IVb'):
##STR00092##
In formula (IVb'), M is a transition metal atom selected from the
groups 8 and 9 in the periodic table, and specifically M is iron or
cobalt.
In formula (IVb'), R.sup.7 to R.sup.13 may be the same or different
and each represent a hydrogen atom, a halogen atom, a hydrocarbon
group, an oxygen-containing group, a nitrogen-containing group, a
boron-containing group, a sulfur-containing group, a
phosphorus-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group, and two or more of these groups may be bound
to each other to form a ring. Each of R.sup.12 and R.sup.13 is
preferably a hydrocarbon group, more preferably an aryl group
substituted with an o-alkyl group.
The halogen atom and hydrocarbon group represented by R.sup.7 to
R.sup.13 in formula (IVb') include the same atoms and groups as
illustrated for R.sup.1 to R.sup.7 in the general formula (I)
above.
The hydrocarbon group may be substituted with an oxygen-containing
group, a nitrogen-containing group, a boron-containing group, a
sulfur-containing group, a phosphorus-containing group, a
silicon-containing group, a germanium-containing group, a
tin-containing group etc., wherein an atomic group characterizing
the substituent group such as the oxygen-containing group is
desirably not directly bound to N in formula (IVb').
The oxygen-containing group, nitrogen-containing group,
boron-containing group, sulfur-containing group,
phosphorus-containing group, heterocyclic compound residue,
silicon-containing group, germanium-containing group and
tin-containing group represented by R.sup.7 to R.sup.13 in formula
(IVb') include the same groups as illustrated for R.sup.1 to
R.sup.7 in the general formula (I) above.
More specific groups of R.sup.7 to R.sup.13 in formula (IVb')
include the more specific groups illustrated above as those of
R.sup.1 to R.sup.7 in the formula (I) above.
In formula (IVb'), n is a number satisfying the valence of M, and
is specifically an integer of 1 to 5, preferably 1 to 4, more
preferably 1 to 3.
In formula (IVb'), X represents a hydrogen atom, a halogen atom, a
hydrocarbon group, an oxygen-containing group, a sulfur-containing
group, a nitrogen-containing group, a boron-containing group, a
phosphorus-containing group, a halogen-containing group, a
heterocyclic compound residue, an aluminum-containing group, a
silicon-containing group, a germanium-containing group or a
tin-containing group.
The halogen atom, hydrocarbon group, oxygen-containing group,
sulfur-containing group, nitrogen-containing group,
boron-containing group, aluminum-containing group,
phosphorus-containing group, halogen-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by X in formula (IVb')
include the same atoms or groups as illustrated for X.sup.1 in the
formula (I) above.
When n is 2 or more, a plurality of groups represented by Xs may be
the same or different, and a plurality of groups represented by Xs
may be bound to one another to form a ring.
Specific examples of the compounds represented by the general
formula (IVb) above are shown below.
##STR00093## ##STR00094## ##STR00095##
In the above-illustrated compounds, iPr indicates an isopropyl
group, tBu indicates a t-butyl group, and Ph indicates a phenyl
group.
In the present invention, transition metal compounds wherein in the
compounds described above, iron was replaced by a non-iron metal
such as rhodium and cobalt selected from the groups 8 to 11 in the
periodic table can also be mentioned.
Compound (a-4)
As the component (A) in the present invention, compound (a-4)
represented by the following general formula (IVc) can be used.
##STR00096##
In formula (IVc), M is a transition metal atom selected from the
groups 3 to 11 in the periodic table, preferably a transition metal
atom selected from the groups 4 and 5 and the groups 8 and 9.
Specifically, M is titanium, zirconium, hafnium, vanadium, niobium,
tantalum, iron, rhenium, osmium, cobalt, rhodium, iridium, nickel,
palladium, copper etc., preferably titanium, zirconium, vanadium,
niobium, tantalum, iron, rhenium, cobalt, rhodium etc., more
preferably titanium, zirconium, vanadium, iron or cobalt.
In formula (IVc), m is an integer of 1 to 6, preferably an integer
of 1 to 4, more preferably an integer of 1 to 3, still more
preferably an integer of 1 to 2.
In formula (IVc), R.sup.1 to R.sup.6 may be the same or different
and each represent a hydrogen atom, a halogen atom, a hydrocarbon
group, an oxygen-containing group, a nitrogen-containing group, a
boron-containing group, a sulfur-containing group, a
phosphorus-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group, and two or more of these groups may be bound
to each other to form a ring such as an aromatic ring, an aliphatic
ring, or a hydrocarbon ring containing a heteroatom such as a
nitrogen atom, a sulfur atom and an oxygen atom. Each of R.sup.5
and R.sup.6 is preferably a hydrocarbon group, more preferably an
aryl group substituted with an alkyl group.
The halogen atom and hydrocarbon group represented by R.sup.1 to
R.sup.6 in formula (IVc) include the same halogen atoms and
hydrocarbon groups as illustrated for R.sup.1 to R.sup.7 in the
formula (I) above.
The hydrocarbon group represented by R.sup.1 to R.sup.6 in formula
(IVc) may be substituted with an oxygen-containing group, a
nitrogen-containing group, a boron-containing group, a
sulfur-containing group, a phosphorus-containing group, a
silicon-containing group, a germanium-containing group, a
tin-containing group etc., wherein an atomic group characterizing
the substituent group such as the oxygen-containing group is
desirably not directly bound to N in formula (IVc).
The hydrocarbon group is particularly a C.sub.1-30, preferably
C.sub.1-20, linear or branched alkyl group such as methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl,
neopentyl, n-hexyl etc.; a C.sub.6-30, preferably C.sub.6-20, aryl
group such as phenyl, naphthyl, biphenylyl, terphenylyl,
phenanthryl, anthryl etc.; and a substituted aryl group substituted
with 1 to 5 substituent atoms or groups such as a halogen atom, a
C.sub.1-30, preferably C.sub.1-20, alkyl group or alkoxy group, a
C.sub.6-30, preferably C.sub.6-20, aryl group or aryloxy group.
In formula (IVc), two or more groups of R.sup.1 to R.sup.6,
preferably adjacent groups, may be bound to each other to form an
aromatic ring, an aliphatic ring, or a hydrocarbon ring containing
a nitrogen atom, a sulfur atom, an oxygen atom etc., and these
rings may further have a substituent group, and particularly
R.sup.3 and R.sup.4 are preferably bound to each other to form an
aromatic ring.
The oxygen-containing group, nitrogen-containing group,
boron-containing group, sulfur-containing group,
phosphorus-containing group, heterocyclic compound residue,
silicon-containing group, germanium-containing group and
tin-containing group represented by R.sup.1 to R.sup.6 in formula
(IVc) include the same groups as illustrated for R.sup.1 to R.sup.7
in the formula (I) above.
More specific groups of R.sup.1 to R.sup.6 in formula (IVc) include
the more specific groups illustrated above as those of R.sup.1 to
R.sup.7 in the formula (I) above.
In formula (IVc), n is a number satisfying the valence of M, and is
specifically an integer of 1 to 5, preferably 1 to 4, more
preferably 1 to 3.
When n is 1, X is an oxygen atom, and when n is 2 or more, at least
one of Xs is an oxygen atom, and other Xs represent a hydrogen
atom, a halogen atom, an oxygen atom, a hydrocarbon group, an
oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group, a boron-containing group, an
aluminum-containing group, a phosphorus-containing group, a
halogen-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group.
The halogen atom, hydrocarbon group, oxygen-containing group,
sulfur-containing group, nitrogen-containing group,
boron-containing group, aluminum-containing group,
phosphorus-containing group, halogen-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by X in formula (IVc)
include the same atoms or groups as illustrated for X.sup.1 in the
formula (I) above.
The hydrocarbon group is preferably a C.sub.1-20 group.
When n is 2 or more, a plurality of groups represented by Xs may be
the same or different, and a plurality of groups represented by Xs
may be bound to one another to form a ring.
Compound (a-4) represented by the general formula (IVc) above is
preferably a compound represented by the following general formula
(IVc'):
##STR00097##
In formula (IVc'), M is a transition metal atom selected from the
groups 4 and 5 and the groups 8 and 9 in the periodic table, and
specifically M is titanium, zirconium, vanadium, niobium, tantalum,
iron or cobalt.
In formula (IVc'), m is an integer of 1 to 6, preferably an integer
of 1 to 4, more preferably an integer of 1 to 3, still more
preferably an integer of 1 to 2.
In formula (IVc'), R.sup.7 to R.sup.13 may be the same or different
and each represent a hydrogen atom, a halogen atom, a hydrocarbon
group, an oxygen-containing group, a nitrogen-containing group, a
boron-containing group, a sulfur-containing group, a
phosphorus-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group, and two or more of these groups may be bound
to each other to form a ring. Each of R.sup.12 and R.sup.13 is
preferably a hydrocarbon group, more preferably an aryl group
substituted with an o-alkyl group.
The halogen atom and hydrocarbon group represented by R.sup.7 to
R.sup.13 in formula (IVc') include the same atoms and groups as
illustrated for R.sup.1 to R.sup.7 in the general formula (I)
above.
The hydrocarbon group may be substituted with an oxygen-containing
group, a nitrogen-containing group, a boron-containing group, a
sulfur-containing group, a phosphorus-containing group, a
silicon-containing group, a germanium-containing group, a
tin-containing group etc., wherein an atomic group characterizing
the substituent group such as the oxygen-containing group is
desirably not directly bound to N in formula (IVc').
The oxygen-containing group, nitrogen-containing group,
boron-containing group, sulfur-containing group,
phosphorus-containing group, heterocyclic compound residue,
silicon-containing group, germanium-containing group and
tin-containing group represented by R.sup.7 to R.sup.13 in formula
(IVc') include the same groups as illustrated for R.sup.1 to
R.sup.7 in the general formula (I) above.
More specific groups of R.sup.7 to R.sup.3 in formula (IVc')
include the more specific groups illustrated above as those of
R.sup.1 to R.sup.7 in the formula (I) above.
In formula (IVc'), n is a number satisfying the valence of M, and
is specifically an integer of 1 to 5, preferably 1 to 4, more
preferably 1 to 3.
When n is 1, X is an oxygen atom, and when n is 2 or more, at least
one of Xs is an oxygen atom, and other Xs represent a hydrogen
atom, a halogen atom, an oxygen atom, a hydrocarbon group, an
oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group, a boron-containing group, a
phosphorus-containing group, a halogen-containing group, a
heterocyclic compound residue, an aluminum-containing group, a
silicon-containing group, a germanium-containing group or a
tin-containing group.
The halogen atom, hydrocarbon group, oxygen-containing group,
sulfur-containing group, nitrogen-containing group,
boron-containing group, aluminum-containing group,
phosphorus-containing group, halogen-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by X in formula (IVc')
include the same atoms or groups as illustrated for X.sup.1 in the
formula (I) above.
When n is 2 or more, a plurality of groups represented by Xs may be
the same or different, and a plurality of groups represented by Xs
may be bound to one another to form a ring.
Compound (a-5)
As the component (A) in the present invention, compound (a-5)
represented by the following general formula (V) can be used.
##STR00098##
In formula (V), M is a transition metal atom selected from the
groups 3 to 6 in the periodic table, preferably the group 4 atom,
and specifically M is titanium, zirconium or hafnium.
In formula (V), R and R'' may be the same or different and each
represent a hydrogen atom, a C.sub.1-50 hydrocarbon group, a
C.sub.1-50 halogenated hydrocarbon group, an organic silyl group,
or a substituent group having at least one atom selected from
nitrogen, oxygen, phosphorus, sulfur and silicon, preferably a
hydrocarbon group.
The C.sub.1-50 hydrocarbon group and C.sub.1-50halogenated
hydrocarbon group represented by R and R' in formula (V) include,
for example, the hydrocarbon group and halogenated hydrocarbon
group illustrated as R.sup.1 to R.sup.7 in the general formula (I)
above; the organic silyl group represented by R and R' includes,
for example, the silicon-containing group illustrated as R.sup.1 to
R.sup.7 in the general formula (I) above; and the substituent group
having at least one atom selected from nitrogen, oxygen,
phosphorus, sulfur and silicon represented by R and R' includes,
for example, the nitrogen-, oxygen-, phosphorus-, sulfur- or
silicon-containing residue out of the nitrogen-containing group,
oxygen-containing group, sulfur-containing group and heterocyclic
compound residue illustrated as R.sup.1 to R.sup.7 in the general
formula (I) above.
In formula (V), n is a number satisfying the valence of M, and is
specifically an integer of 1 to 5, preferably 1 to 4, more
preferably 1 to 3.
In formula (V), Xs may be the same or different and each represent
a hydrogen atom, a halogen atom, an oxygen atom, a C.sub.1-20
hydrocarbon group, a C.sub.1-20 halogenated hydrocarbon group, an
oxygen-containing group, a sulfur-containing group, a
silicon-containing group or a nitrogen-containing group, and Xs may
be bound to each other to form a ring.
The halogen atom, C.sub.1-20 hydrocarbon group,
C.sub.1-20halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group represented by X in formula (V) include,
for example, the halogen atom, hydrocarbon group, halogenated
hydrocarbon group, oxygen-containing group, sulfur-containing
group, silicon-containing group and nitrogen-containing group
illustrated as R.sup.1 to R.sup.7 in the general formula (I)
above.
Specific examples of the compounds represented by the general
formula (V) above are shown below.
##STR00099##
In the above-illustrated compounds, .sup.nBu indicates an n-butyl
group, Me indicates a methyl group, .sup.iPr indicates an isopropyl
group, and Ph indicates a phenyl group.
Compound (a-6)
As the component (A) in the present invention, compound (a-6)
represented by the following general formula (VI) can be used.
##STR00100##
In formula (VI), M is a transition metal atom selected from the
groups 4 and 5 in the periodic table, and specifically Mistitanium,
zirconium, hafnium, vanadium, niobium or tantalum.
In formula (VI), R.sup.1 to R.sup.10 may be the same or different
and each represent a hydrogen atom, a C.sub.1-50 hydrocarbon group,
a C.sub.1-50 halogenated hydrocarbon group, an organic silyl group,
or a hydrocarbon group substituted with a substituent group
containing at least one atom selected from nitrogen, oxygen,
phosphorus, sulfur and silicon, and preferably represent hydrogen
or a hydrocarbon group. The groups represented by R.sup.1 to
R.sup.10 may be bound to each other to form a ring.
The C.sub.1-50 hydrocarbon group and C.sub.1-50 halogenated
hydrocarbon group represented by R.sup.1 to R.sup.10 in formula
(VI) include, for example, the hydrocarbon group and halogenated
hydrocarbon group illustrated as R.sup.1 to R.sup.7 in the general
formula (I) above; the organic silyl group represented by R.sup.1
to R.sup.10 includes, for example, the silicon-containing group
illustrated as R.sup.1 to R.sup.7 in the general formula (I) above;
and the hydrocarbon group substituted with a substituent group
containing at least one atom selected from nitrogen, oxygen,
phosphorus, sulfur and silicon, represented by R.sup.1 to R.sup.10,
includes, for example, the nitrogen-, oxygen-, phosphorus-, sulfur-
or silicon-containing residue out of the nitrogen-containing group,
oxygen-containing group, sulfur-containing group and heterocyclic
compound residue illustrated as R.sup.1 to R.sup.7 in the general
formula (I) above.
In formula (VI), n is a number satisfying the valence of M, and is
specifically an integer of 1 to 5, preferably 1 to 4, more
preferably 1 to 3.
In formula (VI), X represent a hydrogen atom, a halogen atom, an
oxygen atom, a C.sub.1-20 hydrocarbon group, C.sub.1-20 halogenated
hydrocarbon group, an oxygen-containing group, a sulfur-containing
group, a silicon-containing group or a nitrogen-containing group,
preferably a halogen atom. When n is 2 or more, a plurality of
groups represented by Xs may be the same or different.
The halogen atom, C.sub.1-20 hydrocarbon group,
C.sub.1-20halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group represented by X in formula (VI) include,
for example, the halogen atom, hydrocarbon group, halogenated
hydrocarbon group, oxygen-containing group, sulfur-containing
group, silicon-containing group and nitrogen-containing group
illustrated as R.sup.1 to R.sup.7 in the general formula (I)
above.
In formula (VI), Y represents an atom selected from the groups 15
and 16 in the periodic table. Specifically, Y represents a
nitrogen, phosphorus, arsenic, antimony, oxygen or sulfur atom,
preferably a nitrogen or oxygen atom.
Specific examples of the compounds represented by the general
formula (VI) above are shown below.
##STR00101##
In the above-illustrated compounds, Ph indicates a phenyl
group.
Compound (a-7)
As the component (A) in the present invention, compound (a-7)
represented by the following general formula (VII) or (VIII) can be
used.
##STR00102##
In formula (VII) or (VIII), M is a transition metal atom selected
from the groups 4 and 5 in the periodic table, and specifically M
is titanium, zirconium, hafnium, vanadium, niobium or tantalum.
R.sup.1 to R.sup.6 in formula (VII) and R.sup.7 to R.sup.10 in
formula (VIII) may be the same or different and each represent
hydrogen, a C.sub.1-50 hydrocarbon group, a C1 to 50 halogenated
hydrocarbon group, an organic silyl group, or a hydrocarbon group
substituted with a substituent group containing at least one atom
selected from nitrogen, oxygen, phosphorus, sulfur and silicon, and
preferably represent hydrogen or a hydrocarbon group. At least two
groups out of the groups represented by R.sup.1 to R.sup.6 in
formula (VII) and R.sup.7 to R.sup.10 in formula (VIII) may be
bound to each other to form a ring.
The C.sub.1-50 hydrocarbon group and C.sub.1-50halogenated
hydrocarbon group represented by R.sup.1 to R.sup.6 in formula
(VII) and R.sup.7 to R.sup.10 in formula (VIII) include, for
example, the hydrocarbon group and halogenated hydrocarbon group
illustrated as R.sup.1 to R.sup.7 in the general formula (I) above;
the organic silyl group represented by R.sup.1 to R.sup.6 in
formula (VII) and R.sup.7 to R.sup.10 in formula (VIII) includes,
for example, the silicon-containing group illustrated as R.sup.1 to
R.sup.7 in the general formula (I) above; and the hydrocarbon group
substituted with a substituent group containing at least one atom
selected from nitrogen, oxygen, phosphorus, sulfur and silicon,
represented by R.sup.1 to R.sup.6 in formula (VII) and R.sup.7 to
R.sup.10 in formula (VIII), includes, for example, a hydrocarbon
group substituted with the nitrogen-, oxygen-, phosphorus-, sulfur-
or silicon-containing residue out of the nitrogen-containing group,
oxygen-containing group, sulfur-containing group and heterocyclic
compound residue illustrated as R.sup.1 to R.sup.7 in the general
formula (I) above.
In formulae (VII) and (VIII), m is an integer of 1 to 6, preferably
an integer of 1 to 4, more preferably an integer of 1 to 2.
In formulae (VII) and (VIII), n is a number satisfying the valence
of M, and is specifically an integer of 1 to 5, preferably 1 to 4,
more preferably 1 to 3.
In formulae (VII) and (VIII), X represent a hydrogen atom, a
halogen atom, an oxygen atom, a C.sub.1-20 hydrocarbon group, a
C.sub.1-20 halogenated hydrocarbon group, an oxygen-containing
group, a sulfur-containing group, a silicon-containing group or a
nitrogen-containing group, preferably a halogen atom. When n is 2
or more, a plurality of groups represented by Xs may be the same or
different.
The halogen atom, C.sub.1-20 hydrocarbon group,
C.sub.1-20halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group represented by X in formulae (VII) and
(VIII) include, for example, the halogen atom, hydrocarbon group,
halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group illustrated as R.sup.1 to R.sup.7 in the
general formula (I) above.
In formulae (VII) and (VIII), Y represents the group 15 or 16 atom
in the periodic table, preferably the group 15 atom. Specifically,
Y represents nitrogen, phosphorus, arsenic, antimony, oxygen or
sulfur, preferably an oxygen atom.
Specific examples of the compounds represented by the general
formula (VII) or (VIII) above are shown below.
##STR00103##
In the above-illustrated compounds, Me indicates a methyl
group.
Compound (a-8)
As the component (A) in the present invention, compound (a-8)
represented by the following general formula (IX) can be used.
##STR00104##
In formula (IX), M is a transition metal atom selected from the
groups 3 to 6 in the periodic table, preferably the group 4
transition metal. Specifically, M is scandium, yttrium, titanium,
zirconium, hafnium, vanadium, niobium, tantalum, chromium,
molybdenum or tungsten, preferably titanium, zirconium or
hafnium.
In formula (IX), R and R' may be the same or different and each
represent a hydrogen atom, a C.sub.1-50 hydrocarbon group, a
C.sub.1-50 halogenated hydrocarbon group, an organic silyl group,
or a substituent group having at least one atom selected from
nitrogen, oxygen, phosphorus, sulfur and silicon, preferably a
hydrocarbon group.
The C.sub.1-50 hydrocarbon group and C.sub.1-50 halogenated
hydrocarbon group represented by R and R' in formula (IX) include,
for example, the hydrocarbon group and halogenated hydrocarbon
group illustrated as R.sup.1 to R.sup.7 in the general formula (I)
above; the organic silyl group represented by R and R' includes,
for example, the silicon-containing groups illustrated as R.sup.1
to R.sup.7 in the general formula (I) above; and the substituent
group having at least one atom selected from nitrogen, oxygen,
phosphorus, sulfur and silicon represented by R and R' includes,
for example, the nitrogen-, oxygen-, phosphorus-, sulfur- or
silicon-containing residue out of the nitrogen-containing group,
oxygen-containing group, sulfur-containing group and heterocyclic
compound residue illustrated as R.sup.1 to R.sup.7 in the general
formula (I) above.
In formula (IX), m is an integer of 0 to 2, preferably 2.
In formula (IX), n is an integer of 1 to 5, preferably an integer
of 1 to 3.
In formula (IX), A represents an atom selected from the groups 13
to 16 in the periodic table, preferably the group 14 atom in the
periodic table. Specifically, A is boron, carbon, nitrogen, oxygen,
silicon, phosphorus, sulfur, germanium or tin, preferably carbon or
silicon. When n is 2 or more, a plurality of As may be the same or
different.
In formula (IX), E is a substituent group having at least one kind
of atom selected from carbon, hydrogen, oxygen, halogen, nitrogen,
sulfur, phosphorus, boron and silicon, and E is preferably hydrogen
or a carbon atom. When a plurality of groups are represented by Es,
a plurality of groups represented by Es may be the same or
different, and two or more groups represented by Es may be bound to
each other to form a ring.
The substituent group having at least one kind of atom selected
from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur,
phosphorus, boron and silicon, represented by E in formula (IX),
includes the halogen atom, hydrocarbon group, oxygen-containing
group, nitrogen-containing group, boron-containing group,
sulfur-containing group, phosphorus-containing group, heterocyclic
compound residue and silicon-containing group illustrated as
R.sup.1 to R.sup.7 in the general formula (I) above.
In formula (IX), p is an integer of 0 to 4, preferably 2.
In formula (IX), X represents a hydrogen atom, a halogen atom, an
oxygen atom, a C.sub.1-20 hydrocarbon group, a C.sub.1-20
halogenated hydrocarbon group, an oxygen-containing group, a
sulfur-containing group, a silicon-containing group or a
nitrogen-containing group. When p is 2 or more, a plurality of
groups represented by Xs may be the same or different.
The halogen atom, C.sub.1-20 hydrocarbon group,
C.sub.1-20halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group represented by X in formula (IX)
includes, for example, the halogen atom, hydrocarbon group,
halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group illustrated as R.sup.1 to R.sup.7 in the
general formula (I) above.
Specific examples of the compounds represented by the general
formula (IX) above are shown below:
##STR00105## ##STR00106## ##STR00107## ##STR00108## ##STR00109##
##STR00110## ##STR00111## Compound (a-9)
As the component (A) in the present invention, compound (a-9)
represented by the following general formula (X) can be used.
##STR00112##
In formula (X), M is a transition metal atom selected from the
groups 3 to 11 in the periodic table, preferably a transition metal
atom selected from the groups 3 to 6 in the periodic table, more
preferably a transition metal atom selected from the group 4 in the
periodic table. Specifically, M is scandium, yttrium, titanium,
zirconium, hafnium, vanadium, niobium, tantalum, chromium,
molybdenum or tungsten, preferably titanium, zirconium or
hafnium.
In formula (X), A represents an atom selected from the groups 14 to
16 in the periodic table, preferably an atom selected from the
groups 15 and 16. Specifically, A is preferably NR.sup.9,
PR.sup.10, O or S.
In formula (X), m is an integer of 0 to 3, n is an integer of 0 or
1, p is an integer of 1 to 3, and q is a number satisfying the
valence of M, and when m is 0, n is 0, and p is preferably 2.
In formula (X), R.sup.1 to R.sup.10 may be the same or different
and each represent a hydrogen atom, a halogen atom, a C.sub.1-20
hydrocarbon group, a C.sub.1-20 halogenated hydrocarbon group, an
oxygen-containing group, a sulfur-containing group, a
silicon-containing group or a nitrogen-containing group, and two or
more of these groups may be bound to each other to form a ring.
The halogen atom, C.sub.1-20 hydrocarbon group, C.sub.1-20
halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group represented by R.sup.1 to R.sup.10 in
formula (X) include, for example, the halogen atom, hydrocarbon
group, halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group illustrated as R.sup.1 to R.sup.7 in the
general formula (I) above.
In formula (X), X represents a hydrogen atom, a halogen atom, an
oxygen atom, a C.sub.1-20 hydrocarbon group, a C.sub.1-20
halogenated hydrocarbon group, an oxygen-containing group, a
sulfur-containing group, a silicon-containing group or a
nitrogen-containing group. Note that when q is 2 or more, a
plurality of groups represented by Xs may be the same or
different.
The halogen atom, C.sub.1-20 hydrocarbon group, C.sub.1-20
halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group represented by X in formula (X) include,
for example, the halogen atom, hydrocarbon group, halogenated
hydrocarbon group, oxygen-containing group, sulfur-containing
group, silicon-containing group and nitrogen-containing group
illustrated as R.sup.1 to R.sup.7 in the general formula (I)
above.
When m in formula (X) is 1 to 3, Y is a group for bridging a borate
benzene ring with A, and represents carbon, silicon or
germanium.
Examples of compounds represented by the general formula (X) are
shown below.
##STR00113##
In the above-illustrated compounds, .sup.iPr indicates an isopropyl
group, .sup.tBu indicates a tert-butyl group, and Ph indicates a
phenyl group.
Compound (a-10)
As the component (A) in the present invention, compound (a-10)
represented by the following general formula (XIa) can be used.
##STR00114##
In formula (XIa), M is a transition metal atom selected from the
groups 3 to 11 in the periodic table, preferably a transition metal
atom in the groups 3 to 6 in the periodic table, more preferably a
transition metal atom in the groups 4 and 5 in the periodic table,
still more preferably a transition metal atom in the group 4 in the
periodic table. Specifically, M is scandium, yttrium, titanium,
zirconium, hafnium, vanadium, niobium, tantalum, chromium,
molybdenum or tungsten, preferably titanium, zirconium or
hafnium.
In formula (XIa), A and A' may be the same or different and each
represent a C.sub.1-50 hydrocarbon group, a C.sub.1-50 halogenated
hydrocarbon group, a hydrocarbon group having an oxygen-containing
group, a sulfur-containing group or a silicon-containing group, or
a halogenated hydrocarbon group having an oxygen-containing group,
a sulfur-containing group or a silicon-containing group, preferably
a hydrocarbon, more preferably an aryl group substituted with an
alkyl group.
The C.sub.1-50 hydrocarbon group and C.sub.1-50 halogenated
hydrocarbon group represented by A and A' in formula (XIa) include,
for example, the hydrocarbon group and halogenated hydrocarbon
group illustrated as R.sup.1 to R.sup.7 in the general formula (I)
above; the hydrocarbon group having an oxygen-containing group, a
sulfur-containing group or a silicon-containing group, represented
by A and A' includes, for example, the hydrocarbon group having an
oxygen-containing group, a sulfur-containing group or a
silicon-containing group illustrated as R.sup.1 to R.sup.7 in the
general formula (I) above; and the halogenated hydrocarbon group
having an oxygen-containing group, a sulfur-containing group or a
silicon-containing group represented by A and A' includes, for
example, the halogenated hydrocarbon group having an
oxygen-containing group, a sulfur-containing group or a
silicon-containing group illustrated as R.sup.1 to R.sup.7 in the
general formula (I) above.
In formula (XIa), D may be present or absent, and when D is
present, it is a linking group for bridging A to A', and when D is
absent, A and A' are bound to each other via --O-M-O-- only.
D in formula (XIa) is specifically a single bond, a C.sub.1-20
hydrocarbon group, a C.sub.1-20 halogenated hydrocarbon, an oxygen
atom, a sulfur atom or a group represented by R.sup.1R.sup.2Z.
R.sup.1 and R.sup.2 may be the same or different and each represent
a C.sub.1-20 hydrocarbon group or a C.sub.1-20 hydrocarbon group
containing at least one heteroatom, and may be bound to each other
to form a ring, and Z represents a carbon atom, a nitrogen atom, a
sulfur atom, a phosphorus atom or a silicon atom.
In formula (XIa), n is a number satisfying the valence of M, and is
specifically an integer of 1 to 5, preferably 1 to 4, more
preferably 1 to 3.
In formula (XIa), X represents a hydrogen atom, a halogen atom, a
C.sub.1-20 hydrocarbon group, a C.sub.1-20 halogenated hydrocarbon
group, an oxygen-containing group, a sulfur-containing group, a
silicon-containing group or a nitrogen-containing group, and when n
is 2 or more, a plurality of groups represented by Xs may be the
same or different, and a plurality of groups represented by Xs may
be bound to each other to form a ring.
The halogen atom, C.sub.1-20 hydrocarbon group, C.sub.1-20
halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group represented by X in formula (XIa)
include, for example, the halogen atom, hydrocarbon group,
halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group illustrated as R.sup.1 to R.sup.7 in the
general formula (I) above.
Examples of compounds represented by the general formula (XIa) are
shown below.
##STR00115## ##STR00116## ##STR00117##
In the above-illustrated compounds, .sup.tBu indicates a t-butyl
group, and Me indicates a methyl group.
Compound (a-11)
As the component (A) in the present invention, compound (a-11)
represented by the following general formula (XIb) can be used.
##STR00118##
In formula (XIb), M represents a transition metal atom selected
from the groups 3 toll in the periodic table, preferably a
transition metal atom in the groups 3 to 6 in the periodic table,
more preferably a transition metal atom in the groups 4 and 5 in
the periodic table, still more preferably a transition metal atom
in the group 4 in the periodic table. Specifically, M is scandium,
yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum,
chromium, molybdenum or tungsten, more preferably titanium,
zirconium or hafnium.
In formula (XIb), m is an integer of 1 to 6, preferably an integer
of 1 to 4, more preferably an integer of 1 to 3, still more
preferably an integer of 1 to 2.
In formula (XIb), A and A' may be the same or different and each
represent a C.sub.1-50 hydrocarbon group, a C.sub.1-50 halogenated
hydrocarbon group, a hydrocarbon group containing an
oxygen-containing group, a sulfur-containing group or a
silicon-containing group, or a halogenated group containing an
oxygen-containing group, a sulfur-containing group or a
silicon-containing group, preferably a hydrocarbon group, more
preferably an aryl group substituted with an alkyl group.
The C.sub.1-50 hydrocarbon group and C.sub.1-50 halogenated
hydrocarbon group represented by A and A' in formula (XIb)
includes, for example, the hydrocarbon group and halogenated
hydrocarbon group illustrated as R.sup.1 to R.sup.7 in the general
formula (I) above; the hydrocarbon group containing an
oxygen-containing group, a sulfur-containing group or a
silicon-containing group represented by A and A' includes, for
example, the hydrocarbon group containing an oxygen-containing
group, a sulfur-containing group or a silicon-containing group
illustrated as R.sup.1 to R.sup.7 in the general formula (I) above;
and the halogenated hydrocarbon group containing an
oxygen-containing group, a sulfur-containing group or a
silicon-containing group represented by A and A' includes, for
example, the halogenated hydrocarbon group containing an
oxygen-containing group, a sulfur-containing group or a
silicon-containing group illustrated as R.sup.1 to R.sup.7 in the
general formula (I) above.
In formula (XIb), D may be present or absent, and when D is
present, it is a linking group for bridging A to A', and when D is
absent, A and A' are bound to each other via --O-M-O-- only. D is
specifically a single bond, a C.sub.1-20 hydrocarbon group, a
C.sub.1-20 halogenated hydrocarbon, an oxygen atom, a sulfur atom
or a group represented by R.sup.1R.sup.2Z. R.sup.1 and R.sup.2 may
be the same or different and each represent a C.sub.1-20
hydrocarbon group or a C.sub.1-20 hydrocarbon group containing at
least one heteroatom, and may be bound to each other to form a
ring, and Z represents a carbon atom, a nitrogen atom, a sulfur
atom, a phosphorus atom or a silicon atom.
In formula (XIb), n is a number satisfying the valence of M, and is
specifically an integer of 1 to 5, preferably 1 to 4, more
preferably 1 to 3.
When n in formula (XIb) is 1, X is an oxygen atom, and when n is 2
or more, at least one of Xs is an oxygen atom, and other Xs
represent a hydrogen atom, a halogen atom, an oxygen atom, a
C.sub.1-20 hydrocarbon group, a C.sub.1-20 halogenated hydrocarbon
group, an oxygen-containing group, a sulfur-containing group, a
silicon-containing group or a nitrogen-containing group, and when
there are a plurality of groups represented by Xs, a plurality of
groups represented by Xs may be the same or different, and a
plurality of groups represented by Xs may be bound to each other to
form a ring.
The halogen atom, C.sub.1-20 hydrocarbon group, C.sub.1-20
halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group represented by X in formula (XIb)
include, for example, the halogen atom, hydrocarbon group,
halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group illustrated as R.sup.1 to R.sup.7 in the
general formula (I) above.
Compound (a-12)
As the component (A) in the present invention, compound (a-12)
represented by the following general formula (XII) can be used.
##STR00119##
In formula (XII), M represents a transition metal atom in the
groups 3 to 11 in the periodic table, preferably a transition metal
atom in the groups 3 to 6 in the periodic table, more preferably a
transition metal atom in the group 4 in the periodic table.
Specifically, M is scandium, yttrium, titanium, zirconium, hafnium,
vanadium, niobium, tantalum, chromium, molybdenum or tungsten, more
preferably titanium, zirconium or hafnium.
Ys may be the same or different and each represent an atom in the
groups 13 to 15 in the periodic table, and specifically Y
represents carbon, silicon, germanium, nitrogen, phosphorus, oxygen
or sulfur. At least one of Ys is an atom other than carbon.
In formula (XII), m is an integer of 1 to 6, preferably 1 to 4,
more preferably 1 to 3.
In formula (XII), R.sup.1 to R.sup.5 are present when their bound
Ys are each an atom selected from the group 14 in the periodic
table, and R.sup.1 to R.sup.5 may be the same or different and each
represent a hydrogen atom, a halogen atom, a hydrocarbon group, a
halogenated hydrocarbon group, an organic silyl group, or a
hydrocarbon group substituted with a substituent group containing
at least one atom selected from nitrogen, oxygen, phosphorus,
sulfur and silicon, and two or more of these groups may be bound to
each other to form a ring.
The hydrocarbon group and halogenated hydrocarbon group represented
by R.sup.1 to R.sup.5 in formula (XII) include, for example, the
hydrocarbon group and halogenated hydrocarbon group illustrated as
R.sup.1 to R.sup.7 in the general formula (I) above; the organic
silyl group represented by R.sup.1 to R.sup.5 includes, for
example, the silicon-containing group illustrated as R.sup.1 to
R.sup.7 in the general formula (I) above; and the substituent group
having at least one atom selected from nitrogen, oxygen,
phosphorus, sulfur and silicon represented by R.sup.1 to R.sup.5
includes, for example, the nitrogen-, oxygen-, phosphorus-, sulfur-
or nitrogen-containing residue out of the nitrogen-containing
group, oxygen-containing group, sulfur-containing group and
heterocyclic compound residue illustrated as R.sup.1 to R.sup.7 in
the general formula (I) above.
In formula (XII), n is a number satisfying the valence of M, and is
specifically an integer of 1 to 5, preferably 1 to 4, more
preferably 1 to 3.
In formula (XII), X represents a hydrogen atom, a halogen atom, an
oxygen atom, a C.sub.1-20 hydrocarbon group, a C.sub.1-20
halogenated hydrocarbon group, an oxygen-containing group, a
sulfur-containing group, a silicon-containing group or a
nitrogen-containing group, and when n is 2 or more, a plurality of
groups represented by Xs may be the same or different, and a
plurality of groups represented by Xs may be bound to each other to
form a ring.
The halogen atom, C.sub.1-20 hydrocarbon group, C.sub.1-20
halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group represented by X in formula (XII)
include, for example, the halogen atom, hydrocarbon group,
halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group illustrated as R.sup.1 to R.sup.6 in the
general formula (I) above.
Examples of compounds represented by the general formula (XII)
above are shown below.
##STR00120##
In the above-illustrated compounds, .sup.tBu indicates a tert-butyl
group, and Me indicates a methyl group.
Compound (a-13)
As the component (A) in the present invention, compound (a-13)
represented by the following general formula (XIII) can be
used.
##STR00121##
In formula (XIII), M is a transition metal compound in the groups 3
to 11 in the periodic table, preferably a transition metal atom in
the groups 4 to 5. Specifically, M is titanium, zirconium,
vanadium, niobium or tantalum.
In formula (XIII), m is an integer of 1 to 6, preferably 1 to
3.
In formula (XIII), Rs may be the same or different and each
represent a hydrogen atom, a C.sub.1-20 hydrocarbon group and a
C.sub.1-20 halogenated hydrocarbon group, and two or more of these
groups may be bound to each other to form a ring.
In formula (XIII), n is a number satisfying the valence of M, and
is specifically an integer of 1 to 5, preferably 1 to 4, more
preferably 1 to 3.
In formula (XIII), when n is 1, X is an oxygen atom, and when n is
2 or more, at least one of Xs is an oxygen atom, and other Xs
represent a hydrogen atom, a halogen atom, an oxygen atom, a
C.sub.1-20 hydrocarbon group, a C.sub.1-20 halogenated hydrocarbon
group, an oxygen-containing group, a sulfur-containing group, a
silicon-containing group or a nitrogen-containing group. When there
are a plurality of groups represented by Xs, a plurality of groups
represented by Xs may be the same or different, and a plurality of
groups represented by Xs may be bound to each other to form a
ring.
The halogen atom, C.sub.1-20 hydrocarbon group, C.sub.1-20
halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group represented by X in formula (XIII)
include, for example, the halogen atom, hydrocarbon group,
halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group illustrated as R.sup.1 to R.sup.7 in the
general formula (I) above.
In formula (XIII), Y may be present or absent, and when Y is
present, it is the group 15 or 16 atom in the periodic table,
specifically O, S, Se or NR.
The specific structures of these compounds include, but are not
limited to, the followings:
##STR00122## Compound (a-14)
As the component (A) in the present invention, compound (a-14)
represented by the following general formula (XIVa) can be
used.
##STR00123##
In formula (XIVa), M is a transition metal atom selected from the
groups 3 to 7 and 11 in the periodic table, preferably a transition
metal atom selected from the groups 4 and 5.
In formula (XIVa), R.sup.1 to R.sup.4 may be the same or different
and each represent a C.sub.1-50 hydrocarbon group, a C.sub.1-50
halogenated hydrocarbon group, an organic silyl group, or a
hydrocarbon group substituted with a substituent group having at
least one atom selected from nitrogen, oxygen, phosphorus, sulfur
and silicon. Two or more groups out of the groups represented by
R.sup.1 to R.sup.4, preferably adjacent groups, may be bound to
each other to form a ring.
The C.sub.1-50 hydrocarbon group and C.sub.1-50 halogenated
hydrocarbon group represented by R.sup.1 to R.sup.4 in formula
(XIVa) include, for example, the hydrocarbon group and halogenated
hydrocarbon group illustrated as R.sup.1 to R.sup.7 in the general
formula (I) above; the organic silyl group represented by R.sup.1
to R.sup.4 includes, for example, the silicon-containing group
illustrated as R.sup.1 to R.sup.7 in the general formula (I) above;
and the substituent group having at least one atom selected from
nitrogen, oxygen, phosphorus, sulfur and silicon represented by
R.sup.1 to R.sup.4 includes, for example, the nitrogen-, oxygen-,
phosphorus-, sulfur- or silicon-containing residue out of the
nitrogen-containing group, oxygen-containing group,
sulfur-containing group and heterocyclic compound residue
illustrated as R.sup.1 to R.sup.7 in the general formula (I)
above.
In formula (XIVa), n is a number satisfying the valence of M, and
is specifically an integer of 0 to 4.
In formula (XIVa), X represents a hydrogen atom, a halogen atom, a
C.sub.1-20 hydrocarbon group, a C.sub.1-20 halogenated hydrocarbon
group, an oxygen-containing group, a sulfur-containing group, a
silicon-containing group or a nitrogen-containing group, and when n
is 2 or more, a plurality of groups represented by Xs may be the
same or different.
The halogen atom, C.sub.1-20 hydrocarbon group, C.sub.1-20
halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group represented by X in formula (XIVa)
include, for example, the halogen atom, hydrocarbon group,
halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group illustrated as R.sup.1 to R.sup.7 in the
general formula (I) above.
Compound (a-15)
As the component (A) in the present invention, compound (a-15)
represented by the following general formula (XIVb) can be
used.
##STR00124##
In formula (XIVb), M is a transition metal atom selected from the
groups 8 to 10 in the periodic table, preferably nickel, palladium
or platinum.
In formula (XIVb)., R.sup.1 to R.sup.4 may be the same or different
and each represent a C.sub.1-50 hydrocarbon group, a C.sub.1-50
halogenated hydrocarbon group, an organic silyl group, or a
hydrocarbon group substituted with a substituent group having at
least one atom selected from nitrogen, oxygen, phosphorus, sulfur
and silicon. Two or more groups out of the groups represented by
R.sup.1 to R.sup.4, preferably adjacent groups, may be bound to
each other to form a ring.
The C.sub.1-50 hydrocarbon group and C.sub.1-50 halogenated
hydrocarbon group represented by R.sup.1 to R.sup.4 in formula
(XIVb) include, for example, the hydrocarbon group and halogenated
hydrocarbon group illustrated as R.sup.1 to R.sup.7 in the general
formula (I) above; the organic silyl group represented by R.sup.1
to R.sup.4 includes, for example, the silicon-containing group
illustrated as R.sup.1 to R.sup.7 in the general formula (I) above;
and the substituent group having at least one atom selected from
nitrogen, oxygen, phosphorus, sulfur and silicon represented by
R.sup.1 to R.sup.4 includes, for example, the nitrogen-, oxygen-,
phosphorus-, sulfur- or silicon-containing residue out of the
nitrogen-containing group, oxygen-containing group,
sulfur-containing group and heterocyclic compound residue
illustrated as R.sup.1 to R.sup.7 in the general formula (I)
above.
In formula (XIVb), n is a number satisfying the valence of M, and
is specifically an integer of 0 to 4.
In formula (XIVb), X represents a hydrogen atom, a halogen atom, a
C.sub.1-20 hydrocarbon group, a C.sub.1-20 halogenated hydrocarbon
group, an oxygen-containing group, a sulfur-containing group, a
silicon-containing group or a nitrogen-containing group, and when n
is 2 or more, a plurality of groups represented by Xs may be the
same or different.
The halogen atom, C.sub.1-20 hydrocarbon group, C.sub.1-20
halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group represented by X in formula (XIVb)
include, for example, the halogen atom, hydrocarbon group,
halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group illustrated as R.sup.1 to R.sup.7 in the
general formula (I) above. The specific structures of these
compounds are shown below:
##STR00125## ##STR00126## ##STR00127## ##STR00128## Compound
(a-16)
As the component (A) in the present invention, compound (a-16)
represented by the following general formula (XIVc) can be
used.
##STR00129##
In formula (XIVc), M is a transition metal atom selected from the
groups 3 to 10 in the periodic table, preferably nickel, palladium
or platinum.
In formula (XIVc), m is an integer of 1 to 6, preferably an integer
of 1 to 4, more preferably an integer of 1 to 3, still more
preferably an integer of 1 to 2.
In formula (XIVc), R.sup.1 to R.sup.4 may be the same or different
and each represent a C.sub.1-50 hydrocarbon group, a C.sub.1-50
halogenated hydrocarbon group, an organic silyl group, or a
hydrocarbon group substituted with a substituent group containing
at least one atom selected from nitrogen, oxygen, phosphorus,
sulfur and silicon. Two or more groups out of the groups
represented by R.sup.1 to R.sup.4, preferably adjacent groups, may
be bound to each other to form a ring.
The C.sub.1-50 hydrocarbon group and C.sub.1-50 halogenated
hydrocarbon group represented by R.sup.1 to R.sup.4 in formula
(XIVc) include, for example, the hydrocarbon group and halogenated
hydrocarbon group illustrated as R.sup.1 to R.sup.7 in the general
formula (I) above; the organic silyl group represented by R.sup.1
to R.sup.4 includes, for example, the silicon-containing group
illustrated as R.sup.1 to R.sup.7 in the general formula (I) above;
and the substituent group having at least one atom selected from
nitrogen, oxygen, phosphorus, sulfur and silicon represented by
R.sup.1 to R.sup.4 includes, for example, the nitrogen-, oxygen-,
phosphorus-, sulfur- or silicon-containing residue out of the
nitrogen-containing group, oxygen-containing group,
sulfur-containing group and heterocyclic compound residue
illustrated as R.sup.1 to R.sup.7 in the general formula (I)
above.
In formula (XIVc), n is a number satisfying the valence of M, and
is specifically an integer of 1 to 5, preferably 1 to 4, more
preferably 1 to 3.
In formula (XIVc), when n is 1, X is an oxygen atom, and when n is
2 or more, at least one of Xs is an oxygen atom, and other Xs
represent a hydrogen atom, a halogen atom, an oxygen atom, a
C.sub.1-20 hydrocarbon group, a C.sub.1-20 halogenated hydrocarbon
group, an oxygen-containing group, a sulfur-containing group, a
silicon-containing group or a nitrogen-containing group, and when
there are a plurality of groups represented by Xs, a plurality of
groups represented by Xs may be the same or different.
The halogen atom, C.sub.1-20 hydrocarbon group, C.sub.1-20
halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group represented by X in formula (XIVc)
include, for example, the halogen atom, hydrocarbon group,
halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group and
nitrogen-containing group illustrated as R.sup.1 to R.sup.6 in the
general formula (IVa) above.
Compound (a-17)
As the component (A) in the present invention, compound (a-17)
represented by the following general formula (XV) can be used.
##STR00130##
In formula (XV), Y.sup.1 and Y.sup.3 may be the same or different
and each represent an atom selected from the group 15 in the
periodic table.
In formula (XV), Y.sup.2 represents an atom selected from the group
16 in the periodic table.
In formula (XV), R.sup.1 to R.sup.8 may be the same or different
and each represent a hydrogen atom, a halogen atom, a C.sub.1-20
hydrocarbon group, a C.sub.1-20 halogenated hydrocarbon group, an
oxygen-containing group, a sulfur-containing group or a
silicon-containing group, and two or more of these groups may be
bound to each other to form a ring.
The C.sub.1-20 hydrocarbon group and C.sub.1-20 halogenated
hydrocarbon group represented by R.sup.1 to R.sup.8 in formula (XV)
include, for example, the hydrocarbon group and halogenated
hydrocarbon group illustrated as R.sup.1 to R.sup.7 in the general
formula (I) above, and the halogen atom, oxygen-containing group,
sulfur-containing group and silicon-containing group represented by
R.sup.1 to R.sup.8 include, for example, the halogen atom,
oxygen-containing group, sulfur-containing group and
silicon-containing group illustrated as R.sup.1 to R.sup.7 in the
general formula (I) above.
Compound (a-18)
As the component (A) in the present invention, compound (a-18)
represented by the following general formula (XVI) can be used.
##STR00131##
In formula (XVI), M represents a transition metal atom selected
from the groups 3 to 11 in the periodic table, preferably a
transition metal atom in the groups 3 to 6 and 8 to 10, more
preferably a transition metal atom in the group 4, 5 or 6, still
more preferably a metal atom in the group 4 or 5.
In formula (XVI), m is an integer of 1 to 6, preferably an integer
of 1 to 4, more preferably an integer of 1 to 3, still more
preferably an integer of 1 to 2.
In formula (XVI), A represents an oxygen atom, a sulfur atom or a
substituent --R.sup.5-containing nitrogen atom
(--N(R.sup.5)--).
In formula (XVI), D represents --C(R.sup.6)(R.sup.7)--,
Si(R.sup.8)(R.sup.9)--, --P(O)(R.sup.10)--, --P(R.sup.11)--, --SO--
or --S--.
In formula (XVI), Z represents N-binding --R.sup.12 and --R.sup.13,
.dbd.C(R.sup.14)R.sup.15 or .dbd.NR.sup.16.
In formula (XVI), R.sup.1 to R.sup.16 may be the same or different
and each represent a hydrogen atom, a halogen atom, a hydrocarbon
group, an oxygen-containing group, a nitrogen-containing group, a
boron-containing group, a sulfur-containing group, a
phosphorus-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group, and two or more of these groups may be bound
to one another to form a ring, and when m is 2 or more, two groups
out of the groups represented by R.sup.1 to R.sup.16 may be bound
to each other.
The halogen atom, hydrocarbon group, oxygen-containing group,
nitrogen-containing group, boron-containing group,
sulfur-containing group, phosphorus-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by R.sup.1 to R.sup.16
in formula (XVI) include, for example, the same atom or group
illustrated as R.sup.1 to R.sup.7 in the general formula (I)
above.
In formula (XVI), n is a number satisfying the valence of M, and is
specifically an integer of 1 to 5, preferably 1 to 4, more
preferably 1 to 3.
In formula (XVI), X represents a hydrogen atom, a halogen atom, an
oxygen atom, a hydrocarbon group, an oxygen-containing group, a
sulfur-containing group, a nitrogen-containing group, a
boron-containing group, an aluminum-containing group, a
phosphorus-containing group, a halogen-containing group, a
heterocyclic compound residue, a silicon-containing group, a
germanium-containing group or a tin-containing group, and when n is
2 or more, a plurality of groups represented by Xs may be the same
or different, and a plurality of groups represented by Xs may be
bound to each other to form a ring.
The halogen atom, hydrocarbon group, oxygen-containing group,
sulfur-containing group, nitrogen-containing group,
boron-containing group, aluminum-containing group,
phosphorus-containing group, halogen-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by X in formula (XVI)
include, for example, the same atom or group illustrated as X.sup.1
in the general formula (I) above.
Compound (a-19)
As the component (A) in the present invention, compound (a-19)
represented by the following general formula (XVII) or (XVIII) can
be used.
##STR00132##
In formulae (XVII) and (XVIII), M represents a transition metal
atom selected from the groups 3 to 11 in the periodic table,
preferably a transition metal atom in the groups 3 to 6 and 8 to
10, more preferably a transition metal atom in the group 4, 5 or 6,
still more preferably a metal atom in the group 4 or 5.
In formula (XVII), m is an integer of 1 to 3.
In formula (XVIII), m' is an integer of 1 to 6, preferably an
integer of 1 to 4, more preferably an integer of 1 to 3, still more
preferably an integer of 1 to 2.
In formulae (XVII) and (XVIII), E represents a nitrogen atom or a
substituent --R.sup.5-containing carbon atom
(--C(R.sup.5).dbd.)
In formulae (XVII) and (XVIII), G represents an oxygen atom, a
sulfur atom or a substituent --R.sup.6-containing nitrogen atom
(--N(R.sup.6)--).
In formulae (XVII) and (XVIII), R.sup.1 to R.sup.6 may be the same
or different and each represent a hydrogen atom, a halogen atom, a
hydrocarbon group, an oxygen-containing group, a
nitrogen-containing group, a boron-containing group, a
sulfur-containing group, a phosphorus-containing group, a
heterocyclic compound residue, a silicon-containing group, a
germanium-containing group or a tin-containing group, and two or
more of these groups may be bound to one another to form a ring,
and when m in formula (XVII) is 2 or more, two groups out of the
groups represented by R.sup.1 to R.sup.6 may be bound to each
other, and when m in formula (XVIII) is 2 or more, two groups out
of the groups represented by R.sup.1 to R.sup.6 may be bound to
each other.
The halogen atom, hydrocarbon group, oxygen-containing group,
nitrogen-containing group, boron-containing group,
sulfur-containing group, phosphorus-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by R.sup.1 to R.sup.6 in
formulae (XVII) and (XVIII) include, for example, the same atom or
group illustrated as R.sup.1 to R.sup.7 in the general formula (I)
above.
In formulae (XVII) and (XVIII), n is a number satisfying the
valence of M, and is specifically an integer of 1 to 5, preferably
1 to 4, more preferably 1 to 3.
In formulae (XVII) and (XVIII), X represents a hydrogen atom, a
halogen atom, an oxygen atom, a hydrocarbon group, an
oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group, a boron-containing group, an
aluminum-containing group, a phosphorus-containing group, a
halogen-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group, and when n in formulae (XVII) and (XVIII) is
2 or more, a plurality of groups represented by Xs may be the same
or different, and a plurality of groups represented by Xs may be
bound to each other to form a ring.
The halogen atom, hydrocarbon group, oxygen-containing group,
sulfur-containing group, nitrogen-containing group,
boron-containing group, aluminum-containing group,
phosphorus-containing group, halogen-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by X in formulae (XVII)
and (XVIII) include, for example, the same atom or group
illustrated as R.sup.1 to R.sup.7 in the general formula (I)
above.
Compound (a-20)
As the component (A) in the present invention, compound (a-20)
represented by the following general formula (XIX) can be used.
##STR00133##
In formula (XIX), M represents a transition metal atom selected
from the groups 3 to 11 in the periodic table, preferably a
transition metal atom in the groups 3 to 6 and 8 to 10, more
preferably a transition metal atom in the group 4, 5 or 6, still
more preferably a metal atom in the group 4 or 5.
In formula (XIX), m is an integer of 1 to 6, preferably an integer
of 1 to 4, more preferably an integer of 1 to 3, still more
preferably an integer of 1 to 2.
In formula (XIX), A represents an oxygen atom, a sulfur atom or a
substituent --R.sup.5-containing nitrogen atom (--N(R.sup.5)--)
In formula (XIX), B represents N-binding --R.sup.6 and --R.sup.7,
.dbd.C(R.sup.8)R.sup.9 or .dbd.NR.sup.10.
In formula (XIX), R.sup.1 to R.sup.10 may be the same or different
and each represent a hydrogen atom, a halogen atom, a hydrocarbon
group, an oxygen-containing group, a nitrogen-containing group, a
boron-containing group, a sulfur-containing group, a
phosphorus-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group, and two or more of these groups may be bound
to each other to form a ring. When m is 2 or more, one group out of
R.sup.1 to R.sup.10 contained in one ligand may be bound to one
group out of R.sup.1 to R.sup.10 contained in another ligand, and
R.sup.1s, R.sup.2s, R.sup.3s, R.sup.4s, R.sup.5s, R.sup.6s,
R.sup.7s, R.sup.8s, R.sup.9s or R.sup.10s may be the same or
different.
The halogen atom, hydrocarbon group, oxygen-containing group,
nitrogen-containing group, boron-containing group,
sulfur-containing group, phosphorus-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by R.sup.1 to R.sup.10
in formula (XIX) include, for example, the same atom or group
illustrated as R.sup.1 to R.sup.7 in the general formula (I)
above.
In formula (XIX), n is a number satisfying the valence of M, and is
specifically an integer of 1 to 5, preferably 1 to 4, more
preferably 1 to 3.
In formula (XIX), X represents a hydrogen atom, a halogen atom, an
oxygen atom, a hydrocarbon group, an oxygen-containing group, a
sulfur-containing group, a nitrogen-containing group, a
boron-containing group, an aluminum-containing group, a
phosphorus-containing group, a halogen-containing group, a
heterocyclic compound residue, a silicon-containing group, a
germanium-containing group or a tin-containing group, and when n is
2 or more, a plurality of groups represented by Xs may be the same
or different, and a plurality of groups represented by Xs may be
bound to each other to form a ring.
The halogen atom, hydrocarbon group, halogenated hydrocarbon group,
oxygen-containing group, sulfur-containing group,
nitrogen-containing group, boron-containing group,
aluminum-containing group, phosphorus-containing group,
halogen-containing group, heterocyclic compound residue,
silicon-containing group, germanium-containing group and
tin-containing group represented by X in formula (XIX) include, for
example, the same atom or group illustrated as X.sup.1 in the
general formula (I) above.
Compound (a-21)
As the component (A) in the present invention, compound (a-21)
represented by the following general formula (XXa) or (XXIa) can be
used.
##STR00134##
In formulae (XXa) and (XXIa), M represents a transition metal atom
selected from the groups 3 and 4 in the periodic table.
In formulae (XXa) and (XXIa), A.sup.1 represents an oxygen atom, a
sulfur atom or a hydrocarbon-substituted nitrogen atom.
In formulae (XXa) and (XXIa), A.sup.2 represents a
hydrocarbon-substituted oxygen atom, a hydrocarbon-substituted
sulfur atom or a hydrocarbon-substituted nitrogen atom.
In formulae (XXa) and (XXIa), E represents an oxygen atom or a
sulfur atom.
In formulae (XXa) and (XXIa), m is an integer of 1 to 2.
In formulae (XXa) and (XXIa), R.sup.1 to R.sup.5 may be the same or
different and each represent a hydrogen atom, a hydrocarbon group
or a hydrocarbon-substituted silyl group.
In formulae (XXa) and (XXIa), n is a number satisfying the valence
of M, and is specifically an integer of 0 to 5, preferably 0 to 4,
more preferably 0 to 3.
In formulae (XXa) and (XXIa), X represents a hydrogen atom, a
halogen atom, an oxygen atom, a hydrocarbon group, an
oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group, a boron-containing group, an
aluminum-containing group, a phosphorus-containing group, a
halogen-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group, and when n is 2 or more, a plurality of
groups represented by Xs may be the same or different, and a
plurality of groups represented by Xs may be bound to each other to
form a ring.
The halogen atom, hydrocarbon group, oxygen-containing group,
sulfur-containing group, nitrogen-containing group,
boron-containing group, aluminum-containing group,
phosphorus-containing group, halogen-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by X in formulae (XXa)
and (XXIa) include, for example, the same atom or group illustrated
as X.sup.1 in the general formula (I) above.
Compound (a-22)
As the component (A) in the present invention, compound (a-22)
represented by the following general formula (XXb) or (XXIb) can be
used.
##STR00135##
In formulae (XXb) and (XXIb), M represents a transition metal atom
selected from the groups 5 to 11 in the periodic table, preferably
a transition metal atom in the groups 8 to 10 in the periodic
table.
In formulae (XXb) and (XXIb), A.sup.1 represents an oxygen atom, a
sulfur atom or a hydrocarbon-substituted nitrogen atom.
In formulae (XXb) and (XXIb), A.sup.2 represents a
hydrocarbon-substituted oxygen atom, a hydrocarbon-substituted
sulfur atom or a hydrocarbon-substituted nitrogen atom.
In formulae (XXb) and (XXIb), E represents an oxygen atom or a
sulfur atom.
In formulae (XXb) and (XXIb), m is an integer of 1 to 2.
In formulae (XXb) and (XXIb), R.sup.1 to R.sup.5 may be the same or
different and each represent a hydrogen atom, a hydrocarbon group
or a hydrocarbon-substituted silyl group.
In formulae (XXb) and (XXIb), n is a number satisfying the valence
of M, and is specifically an integer of 1 to 5, preferably 1 to 4,
more preferably 1 to 3.
In formulae (XXb) and (XXIb), X represents a hydrogen atom, a
halogen atom, an oxygen atom, a hydrocarbon group, an
oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group, a boron-containing group, an
aluminum-containing group, a phosphorus-containing group, a
halogen-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group, and when n is 2 or more, a plurality of
groups represented by Xs may be the same or different, and a
plurality of groups represented by Xs may be bound to each other to
form a ring.
The halogen atom, hydrocarbon group, oxygen-containing group,
sulfur-containing group, nitrogen-containing group,
boron-containing group, aluminum-containing group,
phosphorus-containing group, halogen-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by X in formulae (XXb)
and (XXIb) include, for example, the same atom or group illustrated
as X.sup.1 in the general formula (I) above.
Compound (a-23)
As the component (A) in the present invention, compound (a-23)
represented by the following general formula (XXII), (XXIII),
(XXIV) or (XXV) can be used.
##STR00136##
In formulae (XXII), (XXIII), (XXIV) and (XXV), M represents a
transition metal atom selected from the groups 3 to 11 in the
periodic table, preferably a transition metal atom in the groups 3
to 6 and 8 to 10, more preferably a transition metal atom in the
group 4, 5 or 6, still more preferably a metal atom in the group 4
or 5.
In formulae (XXII), (XXIII), (XXIV) and (XXV), A represents an
oxygen atom, a sulfur atom or a nitrogen atom. Depending on the
mode of binding to the metal M, A can have a substituent group
R.sup.6.
In formulae (XXII), (XXIII), (XXIV) and (XXV), D represents
--C(R.sup.7)(R.sup.8)--, --Si (R.sup.9)(R.sup.10)--, --CO--,
--SO.sub.2--, --SO-- or --P(O)(OR.sup.11)--.
In formulae (XXII), (XXIII), (XXIV) and (XXV), m is an integer of 1
to 6, preferably an integer of 1 to 4, more preferably an integer
of 1 to 3, still more preferably an integer of 1 to 2.
In formulae (XXII), (XXIII), (XXIV) and (XXV), R.sup.1 to R.sup.11
may be the same or different and each represent a hydrogen atom, a
halogen atom, a hydrocarbon group, an oxygen-containing group, a
nitrogen-containing group, a boron-containing group, a
sulfur-containing group, a phosphorus-containing group, a
heterocyclic compound residue, a silicon-containing group, a
germanium-containing group or a tin-containing group, and two or
more of these groups may be bound to each other to form a ring.
When m is 2 or more, R.sup.1s, R.sup.2s, R.sup.3s, R.sup.4s,
R.sup.5s, R.sup.6s, R.sup.7s, R.sup.8s, R.sup.9s, R.sup.10s or
R.sup.11s may be the same or different, and at least one of groups
represented by R.sup.1 to R.sup.11 contained in one ligand may be
bound to at least one of groups represented by R.sup.1 to R.sup.11
contained in another ligand.
The halogen atom, hydrocarbon group, oxygen-containing group,
nitrogen-containing group, boron-containing group,
sulfur-containing group, phosphorus-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by R.sup.1 to R.sup.11
in formulae (XXII), (XXIII), (XXIV) and (XXV) include, for example,
the same atom or group illustrated as R.sup.1 to R.sup.7 in the
general formula (I) above.
In formulae (XXII), (XXIII), (XXIV) and (XXV), n is a number
satisfying the valence of M, and is specifically an integer of 1 to
5, preferably 1 to 4, more preferably 1 to 3.
In formulae (XXII), (XXIII), (XXIV) and (XXV), X represents a
hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group,
an oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group, a boron-containing group, an
aluminum-containing group, a phosphorus-containing group, a
halogen-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group, and when n is 2 or more, a plurality of
groups represented by Xs may be the same or different, and a
plurality of groups represented by Xs may be bound to each other to
form a ring.
The halogen atom, hydrocarbon group, oxygen-containing group,
sulfur-containing group, nitrogen-containing group,
boron-containing group, aluminum-containing group,
phosphorus-containing group, halogen-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by X in formulae (XXII),
(XXIII), (XXIV) and (XXV) include, for example, the same atom or
group illustrated as X.sup.1 in the general formula (I) above.
Compound (a-24)
As the component (A) in the present invention, compound (a-24)
represented by the following general formula (XXVI), (XXVII),
(XXVIII) or (XXIX) can be used.
##STR00137##
In formulae (XXVI), (XXVII), (XXVIII) and (XXIX), M represents a
transition metal atom selected from the groups 3 to 11 in the
periodic table, preferably a transition metal atom in the groups 3
to 6 and 8 to 10, more preferably a transition metal atom in the
group 4, 5 or 6, still more preferably a metal atom in the group 4
or 5.
In formulae (XXVI), (XXVII), (XXVIII) and (XXIX), m is an integer
of 1 to 6, preferably an integer of 1 to 4, more preferably an
integer of 1 to 3, still more preferably an integer of 1 to 2.
In formulae (XXVI), (XXVII), (XXVIII) and (XXIX), A represents an
oxygen atom, a sulfur atom or a nitrogen atom. Depending on the
mode of binding to the metal M, A can have a substituent group
R.sup.5.
In formulae (XXVI), (XXVII), (XXVIII) and (XXIX), B represents
N-binding groups --R.sup.6 and --R.sup.7, .dbd.NR.sup.8 or
.dbd.CR.sup.9R.sup.10.
In formulae (XXVI), (XXVII), (XXVIII) and (XXIX), R.sup.1 to
R.sup.10 may be the same or different and each represent a hydrogen
atom, a halogen atom, a hydrocarbon group, an oxygen-containing
group, a nitrogen-containing group, a boron-containing group, a
sulfur-containing group, a phosphorus-containing group, a
heterocyclic compound residue, a silicon-containing group, a
germanium-containing group or a tin-containing group, and two or
more of these groups may be bound to each other to form a ring.
When m is 2 or more, two groups out of the groups represented by
R.sup.1 to R.sup.10 may be bound to one another to form a ring, and
Rs may be the same or different.
The halogen atom, hydrocarbon group, oxygen-containing group,
nitrogen-containing group, boron-containing group,
sulfur-containing group, phosphorus-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by R.sup.1 to R.sup.10
in formulae (XXVI), (XXVII), (XXVIII) and (XXIX) include, for
example, the same atom or group illustrated as R.sup.1 to R.sup.7
in the general formula (I) above.
In formulae (XXVI), (XXVII), (XXVIII) and (XXIX), n is a number
satisfying the valence of M, and is specifically an integer of 1 to
5, preferably 1 to 4, more preferably 1 to 3.
In formulae (XXVI), (XXVII), (XXVIII) and (XXIX), X represents a
hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group,
an oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group, a boron-containing group, an
aluminum-containing group, a phosphorus-containing group, a
halogen-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group or a
tin-containing group, and when n is 2 or more, a plurality of
groups represented by Xs may be the same or different, and a
plurality of groups represented by Xs may be bound to each other to
form a ring.
The halogen atom, hydrocarbon group, oxygen-containing group,
sulfur-containing group, nitrogen-containing group,
boron-containing group, aluminum-containing group,
phosphorus-containing group, halogen-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by X in formulae (XXVI),
(XXVII), (XXVIII) and (XXIX) include, for example, the same atom or
group illustrated as X.sup.1 in the general formula (I) above.
Compound (a-25)
As the component (A) in the present invention, compound (a-25)
represented by the following general formula (XXX) can be used.
##STR00138##
In formula (XXX), M represents a transition metal atom selected
from the groups 3 to 11 in the periodic table, preferably a
transition metal atom in the groups 3 to 6 and 8 to 10, more
preferably a transition metal atom in the group 4, 5 or 6, still
more preferably a metal atom in the group 4 or 5.
In formula (XXX), A.sup.1 and A.sup.2 may be the same or different
and each represent a nitrogen atom or a phosphorus atom.
In formula (XXX), Q.sup.1 to Q.sup.6 may be the same or different
and each represent a nitrogen atom, a phosphorus atom, or a
substituent --R.sup.2-containing carbon atom (--C(R.sup.2).dbd.),
and when a plurality of substituent-R.sup.2-containing carbon atoms
are present in Q.sup.1 to Q.sup.6, the R.sup.2s may be the same or
different.
In formula (XXX), R.sup.1 and R.sup.2 may be the same or different
and each represent a hydrogen atom, a halogen atom, a hydrocarbon
group, a heterocyclic compound residue, an oxygen-containing group,
a nitrogen-containing group, a boron-containing group, a
sulfur-containing group, a phosphorus-containing group, a
silicon-containing group, a germanium-containing group or a
tin-containing group, and two or more of these groups may be bound
to each other to form a ring.
The halogen atom, hydrocarbon group, oxygen-containing group,
nitrogen-containing group, boron-containing group,
sulfur-containing group, phosphorus-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by R.sup.1 and R.sup.2
in formula (XXX) include, for example, the same atom or group
illustrated as R.sup.1 to R.sup.7 in the general formula (I)
above.
In formula (XXX), m is an integer of 1 to 6, preferably an integer
of 1 to 4, more preferably an integer of 1 to 3, still more
preferably an integer of 1 to 2. When m is 2 or more, R.sup.1 or
R.sup.11 contained in one ligand may be bound to R.sup.1 or
R.sup.11 contained in another ligand, and R.sup.1s or R.sup.2s may
be the same or different.
In formula (XXX), n is a number satisfying the valence of M, and is
specifically an integer of 1 to 5, preferably 1 to 4, more
preferably 1 to 3.
In formula (XXX), X represents a hydrogen atom, a halogen atom, an
oxygen atom, a hydrocarbon group, an oxygen-containing group, a
sulfur-containing group, a nitrogen-containing group, a
boron-containing group, an aluminum-containing group, a
phosphorus-containing group, a halogen-containing group, a
heterocyclic compound residue, a silicon-containing group, a
germanium-containing group or a tin-containing group, and when n is
2 or more, a plurality of groups represented by Xs may be the same
or different, and a plurality of groups represented by Xs may be
bound to each other to form a ring.
The halogen atom, hydrocarbon group, oxygen-containing group,
sulfur-containing group, nitrogen-containing group,
boron-containing group, aluminum-containing group,
phosphorus-containing group, halogen-containing group, heterocyclic
compound residue, silicon-containing group, germanium-containing
group and tin-containing group represented by X in formula (XXX)
include, for example, the same atom or group illustrated as X.sup.1
in the general formula (I) above.
Compound (a-26)
As the component (A) in the present invention, compound (a-26)
represented by the following general formula (XXXIa) or (XXXIIa)
can be used.
##STR00139##
In formulae (XXXIa) and (XXXIIa), M represents a transition metal
atom selected from the groups 3 to 6 in the periodic table,
preferably a transition metal atom in the groups 4 and 5.
In formulae (XXXIa) and (XXXIIa), R.sup.1 to R.sup.6 may be the
same or different and each represent a hydrogen atom, a hydrocarbon
group, a C.sub.1-20 halogenated hydrocarbon group, an
oxygen-containing group, a sulfur-containing group, a
silicon-containing group, a nitrogen-containing group or a
phosphorus-containing group, and two or more of these groups may be
bound to each other to form a ring.
The hydrocarbon group, C.sub.1-20 halogenated hydrocarbon group,
oxygen-containing group, sulfur-containing group,
silicon-containing group, nitrogen-containing group and
phosphorus-containing group represented by R.sup.1 to R.sup.6 in
formulae (XXXIa) and (XXXIIa) include, for example, the hydrocarbon
group, halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group,
nitrogen-containing group and phosphorus-containing group
illustrated as R.sup.1 to R.sup.7 in the general formula (I)
above.
In formulae (XXXIa) and (XXXIIa), n is a number satisfying the
valence of M, and is specifically an integer of 1 to 5, preferably
1 to 4, more preferably 1 to 3.
In formulae (XXXIa) and (XXXIIa), Xs may be the same or different
and each represent a hydrogen atom, a halogen atom, an oxygen atom,
a C.sub.1-20 hydrocarbon group, a C.sub.1-20 halogenated
hydrocarbon group, an oxygen-containing group or a
sulfur-containing group.
The halogen atom, C.sub.1-20 hydrocarbon group, C.sub.1-20
halogenated hydrocarbon group, oxygen-containing group and
sulfur-containing group represented by X in formulae (XXXIa) and
(XXXIIa) include, for example, the halogen atom, hydrocarbon group,
halogenated hydrocarbon group, oxygen-containing group and
sulfur-containing group illustrated as R.sup.1 to R.sup.7 in the
general formula (I) above.
Compound (a-27)
As the component (A) in the present invention, compound (a-27)
represented by the following general formula (XXXIb) or (XXXIIb)
can be used.
##STR00140##
In formulae (XXXIb) and (XXXIIb), M represents a transition metal
atom selected from the groups 8 to 11 in the periodic table,
preferably a transition metal atom selected from the groups 8 and
9.
In formulae (XXXIb) and (XXXIIb), R.sup.1 to R.sup.6 may be the
same or different and each represent a hydrogen atom, a hydrocarbon
group, a C.sub.1-20 halogenated hydrocarbon group, an
oxygen-containing group, a sulfur-containing group, a
silicon-containing group, a nitrogen-containing group or a
phosphorus-containing group, and two or more of these groups may be
bound to each other to form a ring.
The hydrocarbon group, C.sub.1-20 halogenated hydrocarbon group,
oxygen-containing group, sulfur-containing group,
silicon-containing group, nitrogen-containing group and
phosphorus-containing group represented by R.sup.1 to R.sup.6 in
formulae (XXXIb) and (XXXIIb) include, for example, the hydrocarbon
group, halogenated hydrocarbon group, oxygen-containing group,
sulfur-containing group, silicon-containing group,
nitrogen-containing group and phosphorus-containing group
illustrated as R.sup.1 to R.sup.7 in the general formula (I)
above.
In formulae (XXXIb) and (XXXIIb), n is a number satisfying the
valence of M, and is specifically an integer of 1 to 5, preferably
1 to 4, more preferably 1 to 3.
In formulae (XXXIb) and (XXXIIb), Xs may be the same or different
and each represent a hydrogen atom, a halogen atom, an oxygen atom,
a C.sub.1-20 hydrocarbon group, a C.sub.1-20 halogenated
hydrocarbon group, an oxygen-containing group or a
sulfur-containing group.
The halogen atom, C.sub.1-20 hydrocarbon group, C.sub.1-20
halogenated hydrocarbon group, oxygen-containing group and
sulfur-containing group represented by X in formula (XXXIb) and
(XXXIIb) include, for example, the halogen atom, hydrocarbon group,
halogenated hydrocarbon group, oxygen-containing group and
sulfur-containing group illustrated as R.sup.1 to R.sup.7 in the
general formula (I) above.
In the present invention, the transition metal compound (A) in the
groups 3 to 11, having a ligand containing two or more atoms
selected from a boron atom, a nitrogen atom, an oxygen atom and a
sulfur atom may be carried on the carrier component (B). The
transition metal compound (A) is carried on the carrier component
(B) by mixing the transition metal compound (A) with the carrier
component (B) under stirring in an inert solvent for a
predetermined time and then collecting the mixture by filtration,
during which a heating procedure may be carried out. The inert
solvent includes aromatic hydrocarbons such as benzene, toluene and
xylene, aliphatic saturated hydrocarbons such as hexane, heptane
and decane, alicyclic hydrocarbons such as cyclohexane and
methylcyclopentane, and halogenated hydrocarbons such as ethylene
chloride, chlorobenzene and dichloromethane, or mixtures thereof.
In heating, the temperature is varied depending on the solvent
used, but is usually from a temperature higher the solidification
point of the solvent to 200.degree. C., preferably up to
150.degree. C. The stirring mixing time is varied depending on
temperature, but is usually 30 seconds to 24 hours, preferably 10
minutes to 10 hours. A filtration method used in usual organic
synthesis chemistry can be used in collection by filtration. A cake
component after collection by filtration may be washed as necessary
with the above-mentioned aromatic hydrocarbon or aliphatic
hydrocarbon. The carrier thus obtained also satisfies a feature of
the carrier component of the present invention, that is, the molar
ratio of magnesium atom to aluminum atom (Mg/Al) in the range of
1<Mg/Al.ltoreq.300.0 and the molar ratio of alkoxy group to
aluminum atom (OR/Al) in the range of 0.05<OR/Al<2.0.
As the specific organometallic compound (C) (also referred to
hereinafter as "organometallic compound") used if necessary in the
present invention, the following organometallic compounds in the
groups 1 and 2 and groups 12 and 13 in the periodic table can be
arbitrarily used.
Organoaluminum compounds represented by:
(C-1a) The general formula:
R.sup.a.sub.mAl(OR.sup.b).sub.nH.sub.pX.sub.q
wherein R.sup.a and R.sup.b may be the same or different and each
represent a C.sub.1-20, preferably C.sub.1-10, more preferably
C.sub.1-8, hydrocarbon group, X represents a halogen atom, m is a
number of 0<m.ltoreq.3, n is a number of 0.ltoreq.n<3, p is a
number of 0.ltoreq.p<3, and q is a number of 0.ltoreq.q<3,
and simultaneously m+n+p+q=3. Examples of such compounds include
trimethyl aluminum, triethyl aluminum, triisobutyl aluminum,
trioctyl aluminum, and diisobutyl aluminum hydride.
Group 1 metal in the periodic table/aluminum alkylated complexes
represented by:
(C-1b) The general formula: M.sup.aAlR.sup.a.sub.4
wherein M.sup.a represents Li, Na or K, and R.sup.a represents a
C.sub.1-15, preferably C.sub.1-4, hydrocarbon group. Examples of
such compounds include LiAl (C.sub.2H.sub.5).sub.4, LiAl
(C.sub.7H.sub.15).sub.4 etc.
Dialkyl compounds of the group 2 or 12 metal in the periodic table
represented by:
(C-1c) The general formula: R.sup.aR.sup.bM.sup.b
wherein R.sup.a and R.sup.b may be the same or different and each
represent a C.sub.1-15, preferably C.sub.1-4, hydrocarbon group,
and M.sup.b is Mg, Zn or Cd. Among the specific organometallic
compounds (C) described above, the organoaluminum compound is
preferable, and especially the aluminum compound (C-1a) is
preferable. The organometallic compounds (C-1) may be used alone or
as a mixture of two or more thereof.
One feature of the present invention lies in that a conventionally
used organoaluminum oxy compound or organoboron compound is not
used in combination with a transition metal compound by using the
carrier component of the present invention. Accordingly, at least
one compound selected from (C-1a), (C-1b) and (C-1c) is
satisfactory as an arbitrary component in the olefin polymerization
catalyst, but the following organometallic compounds (C-2) and
(C-3) may be contained as the organometallic compound (C) in the
olefin polymerization catalyst of the present invention to further
improve the olefin polymerization activity.
(C-2) Organoaluminum Oxy Compound
The organoaluminum oxy compound (C-2) used in the present invention
may be aluminoxane known in the art or may be a benzene-insoluble
organoaluminum oxy compound illustrated in JP-A 2-78687.
The aluminoxane known in the art can be produced for example by the
following methods, and is obtained usually as a solution in a
hydrocarbon solvent.
(1) A method in which an organoaluminum compound such as trialkyl
aluminum is added to a hydrocarbon suspension of a compound
containing adsorbed water or a salt containing water of
crystallization, for example magnesium chloride hydrate, copper
sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate
or cerous chloride hydrate, and the adsorbed water or water of
crystallization is reacted with the organoaluminum compound. (2) A
method in which water, ice or water vapor is allowed to act
directly on an organoaluminum compound such as trialkyl aluminum in
a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method in which an organotin oxide such as dimethyltin oxide
or dibutyltin oxide is reacted with an organoaluminum compound such
as trialkyl aluminum in a medium such as decane, benzene or
toluene.
The aluminoxane may contain a small amount of an organic metal
component. From the recovered solution of aluminoxane, a solvent or
unreacted organoaluminum compound is removed by distillation, and
the aluminoxane may be re-dissolved in a solvent or suspended in a
poor solvent for aluminoxane.
The examples of organoaluminum compound used in preparing the
aluminoxane includes the same organoaluminum compound as
illustrated for the organoaluminum compound belonging to the
above-mentioned (B-1a).
Among these, trialkyl aluminum and tricycloalkyl aluminum are
preferable, and trimethyl aluminum is particularly preferable.
The organoaluminum compounds described above are used alone or as a
mixture of two or more thereof.
The benzene-insoluble organoaluminum oxy compound used in the
present invention is preferably insoluble or sparingly soluble in
benzene wherein the Al component dissolved in benzene at 60.degree.
C. is usually 10% or less, preferably 5% or less, particularly
preferably 2% or less, in terms of Al atom. These organoaluminum
oxy compounds (B-2) are used alone or as a mixture of two or more
thereof.
(C-3) Compound which Reacts with a Transition Metal Compound to
Form an Ion Pair
Compound (C-3) which reacts with the transition metal compound (A)
in the present invention to form an ion pair (hereinafter referred
to as "ionized ionic compound") includes Lewis acid, ionic
compounds, borane compounds and carborane compounds described in
JP-A 1-501950, JP-A 1-502036, JP-A 3-179005, JP-A 3-179006, JP-A
3-207703, JP-A 3-207704 and U.S. Pat. No. 5,321,106. Further,
heteropoly compounds and isopoly compounds can also be mentioned.
These ionized ionic compounds (C-3) can be used alone or as a
mixture of two or more thereof.
In the olefin polymerization catalyst of the present invention,
inorganic carriers of SiO.sub.2, Al.sub.2O.sub.3, MgO, ZrO,
TiO.sub.2, B.sub.2O.sub.3, CaO, ZnO, BaO and ThO.sub.2 or organic
carriers of granular or fine particle organic polymers having a
particle diameter of 10 to 300 .mu.m such as polyethylene,
polypropylene, polybutene and polystyrene can be used in addition
to the carrier component (B), the transition metal compound (A) and
the specific organometallic compound (C).
Method of Polymerizing an Olefin, and Polyolefin Obtained by this
Method
The polyolefin of the present invention is a polyolefin having a
bulk density of 0.20 (g/cm.sup.3) or more, which obtained in the
presence of the olefin polymerization catalyst by homopolymerizing
or copolymerizing olefins by the high activity of the catalyst.
The olefin subjected to the polymerization reaction in the present
invention is at least one monomer selected from ethylene and
.alpha.-olefin, and at least one monomer is ethylene or propylene.
The .alpha.-olefin includes C.sub.3-20, preferably C.sub.3-10,
linear or branched .alpha.-olefins, for example, propylene,
1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene,
4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and
1-eicocene. In the polymerization method of the present invention,
mention can be made of C.sub.3-30, preferably C.sub.3-20, cyclic
olefins, for example cyclopentene, cycloheptene, norbornene,
5-methyl-2-norbornene, tetracyclododecene,
2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene;
polar monomers, for example allyl alcohol and
.alpha.,.beta.-unsaturated carboxylic acids such as acrylic acid,
methacrylic acid, fumaric acid, maleic anhydride, itaconic acid,
itaconic anhydride, bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic
anhydride, and metal salts thereof such as sodium salt, potassium
salt, lithium salt, zinc salt, magnesium salt, calcium salt etc.;
.alpha.,.beta.-unsaturated carboxylates such as methyl acrylate,
ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl
acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl
acrylate, methyl methacrylate, ethyl methacrylate, n-propyl
methacrylate, isopropyl methacrylate, n-butyl methacrylate,
isobutyl methacrylate etc.; vinyl esters such as vinyl acetate,
vinyl propionate, vinyl caproate, vinyl caprinate, vinyl laurate,
vinyl stearate, vinyl trifluoroacetate etc.; and unsaturated
glycidyl such as glycidyl acrylate, glycidyl methacrylate,
monoglycidyl itaconate etc. Further, vinyl cyclohexane, diene or
polyene; an aromatic vinyl compound, for example mono- or polyalkyl
styrene such as styrene, o-methyl styrene, m-methyl styrene,
p-methyl styrene, o,p-dimethyl styrene, o-ethyl styrene, m-ethyl
styrene, p-ethyl styrene etc.; a functional group-containing
styrene derivative such as methoxy styrene, ethoxy styrene,
vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate,
hydroxy styrene, o-chlorostyrene, p-chlorostyrene., divinyl benzene
etc.; and 3-phenylpropylene, 4-phenylpropylene,
.alpha.-methylstyrene can be allowed to be present in the reaction
system to allow the polymerization to proceed.
In the method of polymerizing olefins according to the present
invention, olefins are polymerized or copolymerized in the presence
of the olefin polymerization catalyst described above, to give an
olefin polymer.
The polymerization in the present invention can be carried out by
liquid-phase polymerization such as solution polymerization or
suspension polymerization or by gaseous-phase polymerization.
Examples of inert hydrocarbon solvents used in solution
polymerization or suspension polymerization include aliphatic
hydrocarbons such as propane, butane, pentane, hexane, heptane,
octane, decane, dodecane and kerosene; alicyclic hydrocarbons such
as cyclopentane, cyclohexane and methylcyclopentane; aromatic
hydrocarbons such as benzene, toluene and xylene; halogenated
hydrocarbons such as ethylene chloride, chlorobenzene and
dichloromethane, or mixtures thereof, and olefins themselves can
also be used as the solvent.
When the olefin polymerization catalyst described above is used in
polymerization of olefins, the component (A) is used usually in an
amount of 10.sup.-8 to 10.sup.-2 mole, preferably 10.sup.-7 to
10.sup.-3 mole, per L of the reaction volume.
Component (B) is used in such an amount that the molar ratio of the
magnesium atom to the total transition metal atom (M) in component
(B) [Mg/M] is usually 1.0 to 1000, preferably 10 to 800. Component
(C) is used in such an amount that the molar ratio of the metal
atom (M') in component (C) to the total transition metal atom (M)
in component (A) [M'/M] is usually 5 to 5000, preferably 100 to
3000.
The temperature of polymerization of an olefin by using the olefin
polymerization catalyst is usually in the range of -50 to
+200.degree. C., preferably 0 to 170.degree. C. The polymerization
pressure is usually normal pressures to 10 MPa gauge pressure,
preferably normal pressures to 5 MPa gauge pressure, and the
polymerization reaction can be carried out in a batch,
semi-continuous or continuous system. Further, polymerization can
be carried out in two or more stages different in reaction
conditions. The molecular weight of the obtained olefin polymer can
be regulated by allowing hydrogen, an organosilane compound or
another known molecular-weight regulator to be present in the
polymerization system or by changing the polymerization
temperature. Further, the molecular weight can be regulated by
changing the amount of component (A) used.
The polymer obtained by the polymerization method of the present
invention described above is characterized in that its bulk density
is 0.20 (g/cm.sup.3) or more, preferably 0.22 (g/cm.sup.3) or more.
In addition, the polymer is characterized in that the
molecular-weight distribution (Mw/Mn) determined by GPC can be
changed not only by a polymerization process such as multi-stage
polymerization, but can also be regulated by selection of component
(A) and can be changed in the Mw/Mn range of 1 to 150, and the
polymer can be produced so as to adaptable for various uses.
Now, a major analytical method in the present invention, and
methods of measuring the physical properties and properties of
polymers obtained by polymerization of olefins are described.
[Analysis of the Composition of the Carrier Component]
The metal content in the carrier component was determined by plasma
emission mass spectrometry. The halogen content was determined by
potential difference titration, and the alkoxy group content by gas
chromatography.
[Average Particle Diameter of the Carrier Component]
The number-average particle diameter was determined by an optical
transmission sedimentation method using a known Stokes formula
(Equation 1). The unit used was an automatic particle-size
distribution measuring unit (CAPA-300, manufactured by HORIBA,
Ltd.). The dispersant used was a mixed solution of decalin and
triolein (decalin/triolein=1/4 (weight ratio)).
.times..times..eta..times..function..rho..rho..times..omega..times.
##EQU00001## D: Particle diameter of catalyst (cm) .eta..sub.0:
Viscosity coefficient of dispersant (poise) .rho.: Sample density
(g/cm.sup.3) .rho..sub.0: Dispersant density (g/cm.sup.3) t:
Sedimentation time (sec.) X.sub.1: Distance from rotation center to
sedimentation surface (cm) X.sub.2: Distance from rotation center
to measurement surface (cm) .omega.: Rotation angular velocity
(rad/sec.) [Crystallite Size of the Carrier Component]
The crystallite size was determined by measuring the half band
width value of a magnesium chloride (110) face with an X-ray
diffraction unit (RU-300 manufactured by Rigaku Corporation.) and
by applying a known Scherrer's equation (in the equation, 0.9 is
attributable to the constant K). All samples used in measuring
their crystallite size were handled in a nitrogen atmosphere. The
method of measuring the crystallite size by using the Scherrer
formula is described in detail in Essence of Cullity X-Ray
Diffraction (in Japanese) (translated by Gentaro Matsumura)
published by Agne Co., Ltd.
[Weight-Average Molecular Weight (Mw) and Number-Average Molecular
Weight (Mn) of the Polymer]
Calculated from a molecular-weight distribution curve obtained by
Waters model [Alliance GPC 2000] gel permeation chromatography
(high-temperature size-extrusion chromatography). The operation
conditions are as follows:
Mobilephase: o-Dichlorobenzene (Wako Pure Chemical Industries,
Ltd.)
Flow rate of mobile phase: 1 ml/min. Columns: Two columns of
TSK-GEL.RTM. model GMH6-HT and two columns of TSK-GEL.RTM. model
GMH6-HTL. Temperature: 140.degree. C. Sample concentration: 30
mg/20 ml (0.15% (w/v)) Injection volume: 500 .mu.L Detection
method: Detection by a reflectometer integrated in a
chromatographic unit [Intrinsic Viscosity [.eta.] of the
Polymer]
The intrinsic viscosity is a value measured at 135.degree. C. in a
decalin solvent. That is, about 20 g granulated pellets are
dissolved in 15 ml decalin and measured for its specific viscosity
.eta..sub.sp in an oil bath at 135.degree. C. This decalin solution
is diluted with additional 5 ml decalin solvent, and then measured
for its specific viscosity .eta..sub.sp spin the same manner as
above. This diluting procedure is repeated further twice, and the
value of .eta..sub.sp/C upon extrapolation of concentration (C) to
0 is determined as the intrinsic viscosity.
[.eta.]=lim(.eta..sub.sp/C)(C.fwdarw.0) [Melt flow rate
(MFR.sub.2.16)]
A value determined at 190.degree. C. under a loading of 2.16 kg by
a standard method of ASTM D-1238.
[Polymer Bulk Density]
Determined from the weight of a sample in a container having an
internal volume of 100 ml according to JIS K-6721.
EXAMPLES
Hereinafter, the present invention is described in more detail by
reference to the Examples, but the present invention is not limited
to the Examples. The structures of compounds obtained in the
synthesis examples were determined by using 270 MHz .sup.1H-NMR
(JEOL GSH-270), FD-mass spectrometry (JEOL SX-102A) etc.
Example 1
Preparation of Component (b1)
95.2 g (1.0 mole) anhydrous magnesium chloride, 442 ml decane and
390.6 g (3.0 moles) 2-ethylhexyl alcohol were reacted at
130.degree. C. for 2 hours to give a uniform solution (component
(b1)).
Preparation of Component (b1-1)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with 25 ml component (b1) (25 mmol in
terms of magnesium atom) and 100 ml purified decane, and while the
temperature of the solution was kept at 15.degree. C. under
stirring, 26 mmol triethyl aluminum diluted with purified decane
was added dropwise thereto over 30 minutes. Thereafter, the
temperature of the solution was increased to 80.degree. C. over 120
minutes, and the mixture was reacted for additional 60 minutes.
While the temperature was kept at 80.degree. C., 49 mmol triethyl
aluminum diluted with purified decane was again added dropwise
thereto over 30 minutes, and the mixture was further reacted under
heating for 60 minutes. After the reaction was finished, the solids
were collected by filtration and washed sufficiently with toluene,
and 100 ml toluene was added thereto to form a toluene slurry of
component (b1-1). The average particle diameter of the resulting
component (b1-1) was 20 .mu.m.
A part of the component (b1-1) prepared by the above procedure was
dried and examined for its composition, indicating 17.0 weight %
magnesium, 2.9 weight % aluminum, 26.4 weight % 2-ethylhexoxy group
and 49.0 weight % chlorine. Accordingly, the molar ratio of
magnesium to aluminum (Mg/Al) was 6.5, and the molar ratio of
2-ethylhexoxy group to aluminum (OR/Al) was 1.9.
Preparation of Component (b1-1-a2-172)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with purified toluene so as to adjust the
total volume to 154.1 ml and with component (b1-1) in an amount of
10 mmol in term of magnesium atom. While the sample was kept at
25.degree. C. under stirring, 45.9 ml toluene solution (0.001089
mmol/ml) of component (a2-172) below was added dropwise thereto
over 20 minutes. After the mixture was stirred for 1 hour, the
solids were collected by filtration and washed sufficiently with
toluene, and 100 ml purified decane was added thereto to give a
decane slurry of component (b1-1-a2-172).
A part of this slurry was collected to analyze its concentration,
indicating 1.30 mg/mL magnesium and 20.8 .mu.g/mL zirconium.
Accordingly, the content of zirconium atom in 1 g of the component
(b1-1-a2-172) was calculated to be 2.7 mg/g.
From the ICP-MASS spectrometry of a dry sample of the component
(b1-1-a2-172), it was confirmed that 0.28 weight % zirconium atom
was contained. The other components were 17.0 weight % magnesium,
2.8 weight % aluminum, 25.1 weight % 2-ethylhexyl group, and 51.0
weight % chlorine. Accordingly, the molar ratio of magnesium to
aluminum (Mg/Al) was 6.7, and the molar ratio of 2-ethylhexoxy
group to aluminum (OR/Al) was 1.9, and it was confirmed that the
molar ratio was hardly changed from the corresponding molar ratio
of component (b1-1).
##STR00141## Polymerization
500 ml purified heptane was introduced into an SUS autoclave having
an internal volume of 1 liter purged sufficiently with nitrogen,
and the liquid phase and gaseous phase were saturated with ethylene
by blowing ethylene. Thereafter, the heptane was heated to
75.degree. C., and the autoclave was charged in an ethylene
atmosphere with 0.5 mmol triethyl aluminum and the above component
(b1-1-a2-172) (0.0004 mmol in terms of zirconium atom) in this
order. Polymerization was carried out for 60 minutes at an ethylene
pressure of 0.8 MPaG. During the polymerization, the system was
kept at 80.degree. C. and at an ethylene pressure of 0.8 MPaG.
After the polymerization was finished, the reaction product was
washed with a large amount of hexane and collected by filtration
with a glass filter. The resulting polymer was dried under vacuum
for 10 hours to give 66.9 g polyethylene.
The polymerization activity was 167.2 kg/mmol-Zrhr, and the
polymerization activity per g of the component (b1-1-a2-172) was
5.1 kg/g-cathr, and this polyethylene had a [.eta.] value of 16.3
dl/g and a bulk density of 0.24 g/cm.sup.3. The Mw of this
polyethylene as determined by GPC was 1.9.times.10.sup.6, and the
Mw/Mn ratio was 4.1.
Example 2
Preparation of Component (b1-1-a2-140)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with purified toluene so as to adjust the
total volume to 128.4 ml and with component (b1-1) in an amount of
10 mmol in term of magnesium atom. While the sample was kept at
25.degree. C. under stirring, 71.6 ml toluene solution (0.000699
mmol/ml) of component (a2-140) below was added dropwise thereto
over 20 minutes. After the mixture was stirred for 1 hour, the
solids were collected by filtration and washed sufficiently with
toluene, and 100 ml purified decane was added thereto to give a
decane slurry of component (b1-1-a2-140).
A part of the component (b1-1-a2-140) prepared by the above
procedure was dried and examined for its composition, indicating
16.0 weight % magnesium, 2.7 weight % aluminum, 24.0 weight %
2-ethylhexoxy group, 48.0 weight % chlorine and 0.30 weight %
zirconium. Similarly to Example 1, the analytical content of
zirconium agreed well with the theoretical content. The molar ratio
of magnesium to aluminum (Mg/Al) was 6.3, and the molar ratio of
2-ethylhexoxy group to aluminum (OR/Al) was 1.8, and it was
confirmed that similarly to Example 1, the molar ratio hardly
changed from the corresponding molar ratio of the component
(b1-1).
##STR00142## Polymerization
Polymerization was carried out in the same manner as in Example 1
except that in the Polymerization in Example 1, the component
(b1-1-a2-140) prepared above was used in place of the component
(b1-1-a2-172). As a result, 50.9 g polyethylene was obtained.
The polymerization activity was 127.3 kg/mmol-Zrhr, and the
polymerization activity per g of the component (b1-1-a2-140) was
4.2 kg/g-cathr, and this polyethylene had a [.eta.] value of 18.3
dl/g and a bulk density of 0.33 g/cm.sup.3. The Mw of this
polyethylene as determined by GPC was 2.4.times.10.sup.6, and the
Mw/Mn ratio was 5.9.
Example 3
Preparation of Component (b1-1-a2-204)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with purified toluene so as to adjust the
total volume to 125.5 ml and with component (b1-1) in an amount of
10 mmol in term of magnesium atom. While the sample was kept at
25.degree. C. under stirring, 74.5 ml toluene solution (0.000671
mmol/ml) of component (a2-204) below was added dropwise thereto
over 20 minutes. After the mixture was stirred for 1 hour, the
solids were collected by filtration and washed sufficiently with
toluene, and 100 ml purified decane was added thereto to give a
decane slurry of component (b1-1-a2-204).
A part of the component (b1-1-a2-204) prepared by the above
procedure was dried and examined for its composition, indicating
17.0 weight % magnesium, 2.7 weight % aluminum, 24.0 weight %
2-ethylhexoxy group, 50.0 weight % chlorine and 0.31 weight %
zirconium. Accordingly, the molar ratio of magnesium to aluminum
(Mg/Al) was 7.0, and the molar ratio of 2-ethylhexoxy group to
aluminum (OR/Al) was 1.8.
##STR00143## Polymerization
Polymerization was carried out in the same manner as in Example 1
except that in the Polymerization in Example 1, the component
(b1-1-a2-204) prepared above was used in place of the component
(b1-1-a2-172). As a result, 40.3 g polyethylene was obtained.
The polymerization activity was 100.8 kg/mmol-Zrhr, and the
polymerization activity per g of the component (b1-1-a2-204) was
3.4 kg/g-cathr, and this polyethylene had a [.eta.] value of 18.1
dl/g and a bulk density of 0.28 g/cm.sup.3. The Mw of this
polyethylene as determined by GPC was 2.2.times.10.sup.6, and the
Mw/Mn ratio was 7.1.
Example 4
Preparation of Component (b1-1-a2-126)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with purified toluene so as to adjust the
total volume to 153.8 ml and with component (b1-1) in an amount of
10 mmol in term of magnesium atom. While the sample was kept at
25.degree. C. under stirring, 46.2 ml toluene solution (0.001083
mmol/ml) of component (a2-126) below was added dropwise thereto
over 20 minutes. After the mixture was stirred for 1 hour, the
solids were collected by filtration and washed sufficiently with
toluene, and 100 ml purified decane was added thereto to give a
decane slurry of component (b1-1-a2-126).
A part of the component (b1-1-a2-126) prepared by the above
procedure was dried and examined for its composition, indicating
17.0 weight % magnesium, 2.8 weight % aluminum, 25.8 weight %
2-ethylhexoxy group, 51.0 weight % chlorine and 0.31 weight %
zirconium. Accordingly, the molar ratio of magnesium to aluminum
(Mg/Al) was 6.7, and the molar ratio of 2-ethylhexoxy group to
aluminum (OR/Al) was 1.9.
##STR00144## Polymerization
Polymerization was carried out in the same manner as in Example 1
except that in the Polymerization in Example 1, the component
(b1-1-a2-126) (0.001 mmol in terms of zirconium atom) prepared
above was used in place of the component (b1-1-a2-172). As a
result, 20.5 g polyethylene was obtained.
The polymerization activity was 20.5 kg/mmol-Zrhr, and the
polymerization activity per g of the component (b1-1-a2-126) was
0.7 kg/g-cathr, and this polyethylene had a [.eta.] value of 0.5
dl/g and a bulk density of 0.20 g/cm.sup.3. The Mw of this
polyethylene as determined by GPC was 1.1.times.10.sup.4, and the
Mw/Mn ratio was 3.0.
Example 5
Preparation of Component (b1-1-a2-116)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with purified toluene so as to adjust the
total volume to 131.8 ml and with component (b1-1) in an amount of
10 mmol in term of magnesium atom. While the sample was kept at
25.degree. C. under stirring, 68.2 ml toluene solution (0.000734
mmol/ml) of component (a2-116) below was added dropwise thereto
over 20 minutes. After the mixture was stirred for 1 hour, the
solids were collected by filtration and washed sufficiently with
toluene, and 100 ml purified decane was added thereto to give a
decane slurry of component (b1-1-a2-116).
A part of the component (b1-1-a2-116) prepared by the above
procedure was dried and examined for its composition, indicating
17.0 weight % magnesium, 2.8 weight % aluminum, 26.6 weight %
2-ethylhexoxy group, 49.0 weight % chlorine and 0.30 weight %
zirconium. Accordingly, the molar ratio of magnesium to aluminum
(Mg/Al) was 6.7, and the molar ratio of 2-ethylhexoxy group to
aluminum (OR/Al) was 2.0.
##STR00145## Polymerization
Polymerization was carried out in the same manner as in Example 1
except that in the Polymerization in Example 1, the component
(b1-1-a2-116) (0.001 mmol in terms of zirconium atom) prepared
above was used in place of the component (b1-1-a2-172). As a
result, 17.5 g polyethylene was obtained.
The polymerization activity was 17.5 kg/mmol-Zrhr, and the
polymerization activity per g of the component (b1-1-a2-116) was
0.6 kg/g-cathr, and this polyethylene had a [.eta.] value of 20.0
dl/g and a bulk density of 0.31 g/cm.sup.3.
Example 6
Preparation of Component (b1-1-a2-228)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with purified toluene so as to adjust the
total volume to 150.0 ml and with component (b1-1) in an amount of
10 mmol in term of magnesium atom. While the sample was kept at
25.degree. C. under stirring, 50.0 ml toluene solution (0.00100
mmol/ml) of component (a2-228) below was added dropwise thereto
over 20 minutes. After the mixture was stirred for 1 hour, the
solids were collected by filtration and washed sufficiently with
toluene, and 100 ml purified decane was added thereto to give a
decane slurry of component (b1-1-a2-228).
A part of the component (b1-1-a2-228) prepared by the above
procedure was dried and examined for its composition, indicating
18.0 weight % magnesium, 2.6 weight % aluminum, 20.0 weight %
2-ethylhexoxy group, 54.0 weight % chlorine and 0.35 weight %
zirconium. Accordingly, the molar ratio of magnesium to aluminum
(Mg/Al) was 7.7, and the molar ratio of 2-ethylhexoxy group to
aluminum (OR/Al) was 1.6.
##STR00146## Polymerization
Polymerization was carried out in the same manner as in Example 1
except that in the Polymerization in Example 1, the component
(b1-1-a2-228) (0.001 mmol in terms of zirconium atom) prepared
above was used in place of the component (b1-1-a2-172). As a
result, 8.8 g polyethylene was obtained.
The polymerization activity was 8.8 kg/mmol-Zrhr, and the
polymerization activity per g of the component (b1-1-a2-228) was
1.2 kg/g-cathr, and the [.eta.] value of this polyethylene was 0.24
dl/g. The Mw of this polyethylene as determined by GPC was
3.0.times.10.sup.3, and the Mw/Mn ratio was 1.9.
Example 7
Preparation of Component (b1-1-a2-138)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with purified toluene so as to adjust the
total volume to 150.0 ml and with component (b1-1) in an amount of
10 mmol in term of magnesium atom. While the sample was kept at
25.degree. C. under stirring, 50.0 ml toluene solution (0.00100
mmol/ml) of component (a2-138) below was added dropwise thereto
over 20 minutes. After the mixture was stirred for 1 hour, the
solids were collected by filtration and washed sufficiently with
toluene, and 100 ml purified decane was added thereto to give a
decane slurry of component (b1-1-a2-138).
A part of the component (b1-1-a2-138) prepared by the above
procedure was dried and examined for its composition, indicating
18.0 weight % magnesium, 2.5 weight % aluminum, 20.5 weight %
2-ethylhexoxy group, 51.0 weight % chlorine and 0.32 weight %
zirconium. Accordingly, the molar ratio of magnesium to aluminum
(Mg/Al) was 8.0, and the molar ratio of 2-ethylhexoxy group to
aluminum (OR/Al) was 1.7.
##STR00147## Polymerization
Polymerization was carried out in the same manner as in Example 1
except that in the Polymerization in Example 1, the component
(b1-1-a2-138) (0.001 mmol in terms of zirconium atom) prepared
above was used in place of the component (b1-1-a2-172). As a
result, 55.5 g polyethylene was obtained.
The polymerization activity was 55.5 kg/mmol-Zr.hr, and the
polymerization activity per g of the component (b1-1-a2-138) was
2.0 kg/g-cathr, and this polyethylene had a [.eta.] value of 13.7
dl/g and a bulk density of 0.21 g/cm.sup.3. The Mw of this
polyethylene as determined by GPC was 166.8.times.10.sup.4, and the
Mw/Mn ratio was 12.3.
Example 8
Preparation of Component (b1-1-a2-241)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with purified toluene so as to adjust the
total volume to 150.0 ml and with component (b1-1) in an amount of
10 mmol in term of magnesium atom. While the sample was kept at
25.degree. C. under stirring, 50.0 ml toluene solution (0.00100
mmol/ml) of component (a2-241) below was added dropwise thereto
over 20 minutes. After the mixture was stirred for 1 hour, the
solids were collected by filtration and washed sufficiently with
toluene, and 100 ml purified decane was added thereto to give a
decane slurry of component (b1-1-a2-241).
A part of the component (b1-1-a2-241) prepared by the above
procedure was dried and examined for its composition, indicating
18.0 weight % magnesium, 2.5 weight % aluminum, 22.8 weight %
2-ethylhexoxy group, 52.0 weight % chlorine and 0.28 weight %
zirconium. Accordingly, the molar ratio of magnesium to aluminum
(Mg/Al) was 8.0, and the molar ratio of 2-ethylhexoxy group to
aluminum (OR/Al) was 1.9.
##STR00148## in place of the component (b1-1-a2-172). As a result,
22.6 Polymerization
Polymerization was carried out in the same manner as in Example 1
except that in the Polymerization in Example 1, the component
(b1-1-a2-241) (0.001 mmol in terms of zirconium atom) prepared
above was used g polyethylene was obtained.
The polymerization activity was 22.6 kg/mmol-Zrhr, and the
polymerization activity per g of the component (b1-1-a2-241) was
0.7 kg/g-cathr, and this polyethylene had a [.eta.] value of 9.7
dl/g and a bulk density of 0.20 g/cm.sup.3. The Mw of this
polyethylene as determined by GPC was 104.4.times.10.sup.4, and the
Mw/Mn ratio was 23.8.
Example 9
Preparation of Component (b1-1-a2-134)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with component (b1-1) in an amount of 4
mmol in term of magnesium atom and 100 ml purified toluene, and
while the sample was kept at room temperature under stirring, 18.8
ml toluene solution (0.00106 mmol/ml) of component (a2-134) below
was added dropwise thereto over 20 minutes. After the mixture was
stirred for 1 hour, the solids were collected by filtration and
washed sufficiently with toluene, and 50 ml purified decane was
added thereto to give a decane slurry of component
(b1-1-a2-134).
A part of this slurry was collected to analyze its concentration,
indicating 1.59 mg/mL magnesium and 30.0 .mu.g/mL zirconium.
Accordingly, the content of zirconium atom in 1 g of the component
(b1-2-a2-134) was calculated to be 3.2 mg/g.
##STR00149## Polymerization
Polymerization was carried out in the same manner as in Example 1
except that in the Polymerization in Example 1, the component
(b1-1-a2-134) (0.001 mmol in terms of zirconium atom) prepared
above was used in place of the component (b1-1-a2-172). As a
result, 15.0 g polyethylene was obtained.
The polymerization activity was 15.0 kg/mmol-Zrhr, and the
polymerization activity per g of the component (b1-1-a2-241) was
0.5 kg/g-cathr, and this polyethylene had a [.eta.] value of 2.8
dl/g and a bulk density of 0.23 g/cm.sup.3.
Example 10
Preparation of Component (b1-1-a2-195)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with component (b1-1) in an amount of 4
mmol in term of magnesium atom and purified toluene so as to adjust
the total volume to 85.4 ml, and while the sample was kept at room
temperature under stirring, 14.6 ml toluene solution (0.00103
mmol/ml) of component (a2-195) below was added dropwise thereto
over 20 minutes. After the mixture was stirred for 1 hour, the
solids were collected by filtration and washed sufficiently with
toluene, and 50 ml purified decane was added thereto to give a
decane slurry of component (b1-1-a2-195).
A part of this slurry was collected to analyze its concentration,
indicating 1.22 mg/mL magnesium and 21.2 .mu.g/mL zirconium.
Accordingly, the content of zirconium atom in 1 g of the component
(b1-2-a2-195) was calculated to be 3.0 mg/g.
##STR00150## Polymerization
500 ml purified heptane was introduced into an SUS autoclave having
an internal volume of 1 liter purged sufficiently with nitrogen,
and the liquid phase and gaseous phase were saturated with ethylene
by blowing ethylene. Thereafter, the heptane was heated to
75.degree. C., and the autoclave was charged in an ethylene
atmosphere with 0.35 mmol triethyl aluminum and the above component
(b1-1-a2-195) (0.00035 mmol in terms of zirconium atom) in this
order. Polymerization was carried out for 60 minutes at an ethylene
pressure of 0.8 MPaG. During the polymerization, the system was
kept at 80.degree. C. and at an ethylene pressure of 0.8 MPaG.
After the polymerization was finished, the reaction product was
washed with a large amount of hexane and collected by filtration
with a glass filter. The resulting polymer was dried under vacuum
for 10 hours to give 41.2 g polyethylene.
The polymerization activity was 160.6 kg/mmol-Zrhr, and the
polymerization activity per g of the component (b1-1-a2-195) was
3.9 kg/g-cathr, and this polyethylene had a [.eta.] value of 17.2
dl/g and a bulk density of 0.28 g/cm.sup.3. [Example 11]
Preparation of Component (b1-2)
A flask having an internal volume of 400 ml purged sufficiently
with nitrogen was charged with 12.5 ml component (b1) (12.5 mmol in
terms of magnesium atom) and 200 ml purified decane, and while the
temperature of the solution was kept at 15.degree. C. under
stirring, 13 mmol triethyl aluminum diluted with purified decane
was added dropwise thereto over 30 minutes. Thereafter, the
temperature of the solution was increased to 80.degree. C. over 120
minutes, and the mixture was reacted for additional 60 minutes.
While the temperature was kept at 80.degree. C., 24.5 mmol triethyl
aluminum diluted with purified decane was again added dropwise
thereto over 30 minutes, and the mixture was further reacted under
heating for 60 minutes. After the reaction was finished, the solids
were collected by filtration and washed sufficiently with toluene,
and 50 ml toluene was added thereto to form a toluene slurry of
component (b1-2). The average particle diameter of the resulting
component (b1-2) was 20 .mu.m.
A part of the component (b1-2) prepared by the above procedure was
dried and examined for its composition, indicating 18.0 weight %
magnesium, 26.0 weight % aluminum, 21.4 weight % 2-ethylhexoxy
group and 52.0 weight % chlorine. Accordingly, the molar ratio of
magnesium to aluminum (Mg/Al) was 7.7, and the molar ratio of
2-ethylhexoxy group to aluminum (OR/Al) was 1.7.
Preparation of Component (b1-2-a2-172)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with component (b1-2) in an amount of 3
mmol in term of magnesium atom and purified toluene so as to adjust
the total volume to 85.1 ml, and while the sample was kept at room
temperature under stirring, 14.9 ml toluene solution (0.001005
mmol/ml) of component (a2-172) below was added dropwise thereto
over 20 minutes. After the mixture was stirred for 1 hour, the
solids were collected by filtration and washed sufficiently with
toluene, and 50 ml purified decane was added thereto to give a
decane slurry of component (b1-2-a2-172).
A part of this slurry was collected to analyze its concentration,
indicating 1.07 mg/mL magnesium and 26.5 .mu.g/mL zirconium.
Accordingly, the content of zirconium atom in 1 g of the component
(b1-2-a2-172) was calculated to be 4.5 mg/g.
Polymerization
Polymerization was carried out in the same manner as in Example 12
except that in the Polymerization in Example 12, the component
(b1-2-a2-172) prepared above was used in place of the component
(b1-1-a2-195). As a result, 57.2 g polyethylene was obtained.
The polymerization activity was 163.3 kg/mmol-Zrhr, and the
polymerization activity per g of the component (b2-1-a2-172) was
8.1 kg/g-cathr, and this polyethylene had a [.eta.] value of 17.4
dl/g and a bulk density of 0.27 g/cm.sup.3.
Example 12
Preparation of Component (b2)
95.2 g (1.0 mole) anhydrous magnesium chloride, 551 ml decane and
325.5 g (2.5 moles) 2-ethylhexyl alcohol were reacted at
130.degree. C. for 2 hours to give a uniform solution (component
(b2)).
Preparation of Component (b2-1)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with 25 ml component (b2) (25 mmol in
terms of magnesium atom) and 100 ml purified decane, and while the
temperature of the solution was kept at 15.degree. C. under
stirring, 25 mmol triethyl aluminum diluted with purified decane
was added dropwise thereto over 30 minutes. Thereafter, the
temperature of the solution was increased to 80.degree. C. over 120
minutes, and the mixture was reacted for additional 60 minutes.
While the temperature was kept at 80.degree. C., 37.5 mmol triethyl
aluminum diluted with purified decane was again added dropwise
thereto over 30 minutes, and the mixture was further reacted under
heating for 60 minutes. After the reaction was finished, the solids
were collected by filtration and washed sufficiently with toluene,
and 100 ml toluene was added thereto to form a toluene slurry of
component (b2-1). The average particle diameter of the resulting
component (b2-1) was 9 .mu.m.
A part of the component (b2-1) prepared by the above procedure was
dried and examined for its composition, indicating 18.0 weight %
magnesium, 2.3 weight % aluminum, 19.0 weight % 2-ethylhexoxy group
and 54.0 weight % chlorine. Accordingly, the molar ratio of
magnesium to aluminum (Mg/Al) was 8.7, and the molar ratio of
2-ethylhexoxy group to aluminum (OR/Al) was 1.6.
Preparation of Component (b2-1-a2-172)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with component (b2-1) in an amount of 4
mmol in term of magnesium atom and purified toluene so as to adjust
the total volume to 85.4 ml, and while the sample was kept at room
temperature under stirring, 14.6 ml toluene solution (0.001029
mmol/ml) of component (a2-172) below was added dropwise thereto
over 20 minutes. After the mixture was stirred for 1 hour, the
solids were collected by filtration and washed sufficiently with
toluene, and 50 ml purified decane was added thereto to give a
decane slurry of component (b2-1-a2-172).
A part of this slurry was collected to analyze its concentration,
indicating 1.26 mg/mL magnesium and 29.0 .mu.g/mL zirconium.
Accordingly, the content of zirconium atom in 1 g of the component
(b2-1-a2-172) was calculated to be 4.1 mg/g.
Polymerization
Polymerization was carried out in the same manner as in Example 10
except that in the Polymerization in Example 10, the component
(b2-1-a2-172) prepared above was used in place of the component
(b1-1-a2-195). As a result, 55.9 g polyethylene was obtained.
The polymerization activity was 159.7 kg/mmol-Zrhr, and the
polymerization activity per g of the component (b2-1-a2-172) was
7.2 kg/g-cathr, and this polyethylene had a [.eta.] value of 17.2
dl/g and a bulk density of 0.29 g/cm.sup.3.
Example 13
Preparation of Component (b1-3)
A flask having an internal volume of 200 mL purged sufficiently
with nitrogen was charged with 25 mL component (b1) (25 mmol in
terms of magnesium atom) and 100 mL purified toluene, and while the
temperature of the solution was kept at -20.degree. C. under
stirring, 26 mmol triethyl aluminum diluted with toluene was added
dropwise thereto over 30 minutes. Thereafter, the temperature of
the solution was increased to 80.degree. C. over 130 minutes, and
the mixture was reacted for 1 hour. While the temperature was kept
at 80.degree. C., 250 mmol triethyl aluminum diluted with toluene
was again added dropwise thereto over 30 minutes, and the mixture
was further reacted under heating for 1 hour. After the reaction
was finished, the solids were collected by filtration and washed
sufficiently with toluene, and 100 mL toluene was added thereto to
form a toluene slurry of component (b1-3). The average particle
diameter of the resulting component (b1-3) was 11 .mu.m.
A part of the component (b1-3) prepared by the above procedure was
dried and examined for its composition, indicating 25.0 weight %
magnesium, 0.6 weight % aluminum, 2.6 weight % 2-ethylhexoxy group
and 71.0 weight % chlorine. Accordingly, the molar ratio of
magnesium to aluminum (Mg/Al) was 46.3, and the molar ratio of
2-ethylhexoxy group to aluminum (OR/Al) was 0.9.
Preparation of Component (b1-3-a2-172)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with purified toluene so as to adjust the
total volume to 85.3 mL and with component (b1-3) in an amount of 3
mmol in term of magnesium atom. While the sample was kept at
25.degree. C. under stirring, 14.7 mL toluene solution (0.001021
mmol/ml) of component (a2-172) above was added dropwise thereto
over 20 minutes. After the mixture was stirred for 1 hour, the
solids were collected by filtration and washed sufficiently with
toluene, and decane was added thereto to give a decane slurry of
component (b1-3-a2-172).
A part of this slurry was collected to analyze its concentration,
indicating 1.05 mg/mL magnesium and 24.0 .mu.g/mL zirconium.
Accordingly, the content of zirconium atom in 1 g of the component
(b1-3-a2-172) was calculated to be 5.72 mg/g.
Polymerization
Polymerization was carried out in the same manner as in Example 10
except that in the Polymerization in Example 10, the component
(b1-3-a2-172) prepared above was used in place of the component
(b1-1-a2-195). As a result, 37.8 g polyethylene was obtained.
The polymerization activity was 108.1 kg/mmol-Zrhr, and the
polymerization activity per g of the component (b1-3-a2-172) was
6.8 kg/g-cathr, and this polyethylene had a [.eta.] value of 16.6
dl/g and a bulk density of 0.40 g/cm.sup.3.
Example 14
Preparation of Component (b1-4)
A flask having an internal volume of 200 mL purged sufficiently
with nitrogen was charged with 25 mL component (b1) (25 mmol in
terms of magnesium atom) prepared in Example 1 and with 100 mL
anhydrous 1,2-dichlorobenzene, and while the temperature of the
solution was kept at 0.degree. C. under stirring, 26 mmol triethyl
aluminum diluted with anhydrous 1,2-dichlorobenzene was added
dropwise thereto over 30 minutes. Thereafter, the temperature of
the solution was increased to 80.degree. C. over 150 minutes, and
the mixture was reacted for 1 hour. While the temperature was kept
at 80.degree. C., 175 mmol triethyl aluminum diluted with anhydrous
1,2-dichlorobenzene was again added dropwise thereto over 30
minutes, and the mixture was further reacted under heating for 1
hour. After the reaction was finished, the solids were collected by
filtration and washed sufficiently with toluene, and 100 mL toluene
was added thereto to form a toluene slurry of component (b1-4). The
average particle diameter of the resulting component (b1-4) was 8
.mu.m.
A part of the component (b1-4) prepared by the above procedure was
dried and examined for its composition, indicating 24.0 weight %
magnesium, 0.6 weight % aluminum, 4.8 weight % 2-ethylhexoxy group
and 68.0 weight % chlorine. Accordingly, the molar ratio of
magnesium to aluminum (Mg/Al) was 44.4, and the molar ratio of
2-ethylhexoxy group to aluminum (OR/Al) was 1.66.
Preparation of Component (b1-4-a2-172)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with purified toluene and component
(b1-4) in an amount of 3 mmol in term of magnesium atom, so as to
adjust the total volume to 85.2 mL. While the sample was kept at
25.degree. C. under stirring, 14.8 mL toluene solution (0.001014
mmol/mL) of the component (a2-172) used in Example 1 was added
dropwise thereto over 20 minutes. After the mixture was stirred for
1 hour, the solids were collected by filtration and washed
sufficiently with toluene, and decane was added thereto to give a
decane slurry of component (b1-4-a2-172).
A part of this slurry was collected to analyze its concentration,
indicating 1.21 mg/mL magnesium and 30.2 .mu.g/mL zirconium.
Accordingly, the content of zirconium atom in 1 g of the component
(b1-4-a2-172) was calculated to be 6.01 mg/g.
Polymerization
Polymerization was carried out in the same manner as in Example 10
except that in the Polymerization in Example 10, the component
(b1-4-a2-172) prepared above was used in place of the component
(b1-1-a2-195). As a result, 70.3 g polyethylene was obtained.
Accordingly, the polymerization activity was 200.8 kg/mmol-Zrhr,
and the polymerization activity per g of the component
(b1-4-a2-172) was 13.2 kg/g-cathr, and this polyethylene had a
[.eta.] value of 16.2 dl/g and a bulk density of 0.34
g/cm.sup.3.
Example 15
Preparation of Component (b1-5)
A flask having an internal volume of 400 mL purged sufficiently
with nitrogen was charged with 25 mL component (b1) (25 mmol in
terms of magnesium atom) prepared in Example 1 and 100 mL purified
toluene, and while the temperature of the solution was kept at
0.degree. C. under stirring, 13 mmol triethyl aluminum diluted with
toluene was added dropwise thereto over 15 minutes. Thereafter, the
temperature of the solution was increased to 105.degree. C. over
110 minutes, and the mixture was reacted for 2 hours. Then, this
reaction solution was cooled to -20.degree. C., and while the
temperature of the solution was kept at -20.degree. C. under
cooling, 13 mmol triethyl aluminum diluted with toluene was again
added dropwise thereto over 15 minutes. Thereafter, the temperature
of the solution was increased to 105.degree. C. over 200 minutes,
and the mixture was reacted for 1 hour. Thereafter, the reaction
mixture was cooled again to -20.degree. C., and charged with 13
mmol triethyl aluminum in the same manner as in the above
procedure, and the temperature of the mixture was increased to
105.degree. C. After the mixture was reacted at 105.degree. C. for
1 hour, 162 mmol triethyl aluminum diluted with toluene was added
dropwise thereto over 30 minutes, and the mixture was reacted for
additional 1 hour under heating. After the reaction was finished,
the solids were collected by filtration and washed sufficiently
with toluene, and 100 mL toluene was added thereto to form a
toluene slurry of component (b1-5). The average particle diameter
of the resulting component (b1-5) was 16 .mu.m.
A part of the component (b1-5) prepared by the above procedure was
dried and examined for its composition, indicating 26.0 weight %
magnesium, 0.4 weight % aluminum, 0.6 weight % 2-ethylhexoxy group
and 72.0 weight % chlorine. Accordingly, the molar ratio of
magnesium to aluminum (Mg/Al) was 72.2, and the molar ratio of
2-ethylhexoxy group to aluminum (OR/Al) was 0.31.
Preparation of Component (b1-5-a2-172)
A flask having an internal volume of 200 mL purged sufficiently
with nitrogen was charged with purified toluene and component
(b1-5) in an amount of 3 mmol in term of magnesium atom, so as to
adjust the total volume to 85.5 mL. While the sample was kept at
25.degree. C. under stirring, 14.5 mL toluene solution (0.001032
mmol/ml) of the component (a2-172) used in Example 1 was added
dropwise thereto over 20 minutes. After the mixture was stirred for
1 hour, the solids were collected by filtration and washed
sufficiently with toluene, and decane was added thereto to give a
decane slurry of component (b1-5-a2-172).
A part of this slurry was collected to analyze its concentration,
indicating 1.30 mg/mL magnesium and 28.4 .mu.g/mL zirconium.
Accordingly, the content of zirconium atom in 1 g of the component
(b1-5-a2-172) was calculated to be 5.67 mg/g.
Polymerization
Polymerization was carried out in the same manner as in Example 10
except that in the Polymerization in Example 10, the component
(b1-5-a2-172) prepared above was used in place of the component
(b1-1-a2-195). As a result, 53.1 g polyethylene was obtained.
Accordingly, the polymerization activity was 151.6 kg/mmol-Zrhr,
and the polymerization activity per g of the component
(b1-5-a2-172) was 9.4 kg/g-cathr, and this polyethylene had a
[.eta.] value of 16.4 dl/g and a bulk density of 0.37
g/cm.sup.3.
Example 16
Preparation of Component (b1-6)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with 25 ml component (b1) (25 mmol in
terms of magnesium atom) and 100 ml anhydrous 1,2-dichlorobenzene,
and while the temperature of the solution was kept at 15.degree. C.
under stirring, 26 mmol triethyl aluminum diluted with purified
decane was added dropwise thereto over 30 minutes. Thereafter, the
temperature of the solution was increased to 80.degree. C. over 120
minutes, and the mixture was reacted for additional 60 minutes.
While the temperature was kept at 80.degree. C., 49 mmol triethyl
aluminum diluted with purified decane was again added dropwise
thereto over 30 minutes, and the mixture was further reacted under
heating for 60 minutes. After the reaction was finished, the solids
were collected by filtration and washed sufficiently with toluene,
and 50 ml toluene was added thereto to form a toluene slurry of
component (b1-6). The average particle diameter of the resulting
component (b1-6) was 7 .mu.m.
A part of the component (b1-6) prepared by the above procedure was
dried and examined for its composition, indicating 19.0 weight %
magnesium, 2.5 weight % aluminum, 19.1 weight % 2-ethylhexoxy group
and 54.0 weight % chlorine. Accordingly, the molar ratio of
magnesium to aluminum (Mg/Al) was 8.4, and the molar ratio of
2-ethylhexoxy group to aluminum (OR/Al) was 1.6.
Preparation of Component (b1-6-a2-172)
A flask having an internal volume of 200 mL purged sufficiently
with nitrogen was charged with purified toluene and component
(b1-6) in an amount of 3 mmol in term of magnesium atom, so as to
adjust the total volume to 85.3 mL. While the sample was kept at
25.degree. C. under stirring, 14.7 mL toluene solution (0.001018
mmol/mL) of the component (a2-172) used in Example 1 was added
dropwise thereto over 20 minutes. After the mixture was stirred for
1 hour, the solids were collected by filtration and washed
sufficiently with toluene, and decane was added thereto to give a
decane slurry of component (b1-6-a2-172).
A part of this slurry was collected to analyze its concentration,
indicating 1.30 mg/mL magnesium and 28.4 .mu.g/mL zirconium.
Accordingly, the content of zirconium atom in 1 g of the component
(b1-6-a2-172) was calculated to be 5.67 mg/g.
Polymerization
Polymerization was carried out in the same manner as in Example 10
except that in the Polymerization in Example 10, the component
(b1-6-a2-172) prepared above was used in place of the component
(b1-1-a2-195). As a result, 60.5 g polyethylene was obtained.
Accordingly, the polymerization activity was 173.0 kg/mmol-Zrhr,
and the polymerization activity per g of the component
(b1-6-a2-172) was 9.8 kg/g-cathr, and this polyethylene had a
[.eta.] value of 17.2 dl/g and a bulk density of 0.22
g/cm.sup.3.
Example 17
Preparation of Component (b1-7)
Component (b1-7) was prepared in the same manner as in Example 16
except that in the Preparation of component (b1-6) in Example 16,
chlorobenzene was used in place of anhydrous
1,2-dichlorobenzene.
The average particle diameter of the prepared component (b1-7) was
5 .mu.m, and a part thereof was dried and examined for its
composition, indicating 18.0 weight % magnesium, 2.6 weight %
aluminum, 20.4 weight % 2-ethylhexoxy group and 52.0 weight %
chlorine. Accordingly, the molar ratio of magnesium to aluminum
(Mg/Al) was 7.7, and the molar ratio of 2-ethylhexoxy group to
aluminum (OR/Al) was 1.6.
Preparation of Component (b1-7-a2-172)
A flask having an internal volume of 200 mL purged sufficiently
with nitrogen was charged with purified toluene and component
(b1-7) in an amount of 3 mmol in term of magnesium atom, so as to
adjust the total volume to 85.7 mL. While the sample was kept at
25.degree. C. under stirring, 14.3 ml toluene solution (0.001047
mmol/mL) of the component (a2-172) used in Example 1 was added
dropwise thereto over 20 minutes. After the mixture was stirred for
1 hour, the solids were collected by filtration 1 and washed
sufficiently with toluene, and decane was added thereto to give a
decane slurry of component (b1-7-a2-172).
A part of this slurry was collected to analyze its concentration,
indicating 1.30 mg/mL magnesium and 28.4 .mu.g/mL zirconium.
Accordingly, the content of zirconium atom in 1 g of the component
(b1-7-a2-172) was calculated to be 5.67 mg/g.
Polymerization
Polymerization was carried out in the same manner as in Example 10
except that in the Polymerization in Example 10, the component
(b1-7-a2-172) prepared above was used in place of the component
(b1-1-a2-195). As a result, 58.6 g polyethylene was obtained.
Accordingly, the polymerization activity was 167.5 kg/mmol-Zrhr,
and the polymerization activity per g of the component
(b1-7-a2-172) was 8.4 kg/g-cathr, and this polyethylene had a
[.eta.] value of 18.1 dl/g and a bulk density of 0.23
g/cm.sup.3.
Example 18
Preparation of Component (b3)
95.2 g (1.0 mole) anhydrous magnesium chloride, 582 ml anhydrous
1,2-dichlorobenzene and 306.0 g (2.35 moles) 2-ethylhexyl alcohol
were reacted at 130.degree. C. for 2 hours to give a uniform
solution (component (b3)).
Preparation of Component (b3-1)
A flask having an internal volume of 200 mL purged sufficiently
with nitrogen was charged with 25 mL component (b3) (25 mmol in
terms of magnesium atom) and 100 mL anhydrous 1,2-dichlorobenzene,
and while the temperature of the solution was kept at 0.degree. C.
under stirring, 26 mmol triethyl aluminum diluted with anhydrous
1,2-dichlorobenzene was added dropwise thereto over 30 minutes.
Thereafter, the temperature of the solution was increased to
100.degree. C. over 200 minutes, and the mixture was reacted for 1
hour. While the temperature was kept at 100.degree. C., 175 mmol
triethyl aluminum diluted with anhydrous 1,2-dichlorobenzene was
again added dropwise thereto over 30 minutes, and the mixture was
further reacted under heating for 1 hour. After the reaction was
finished, the solids were collected by filtration and washed
sufficiently with toluene, and 100 mL toluene was added thereto to
form a toluene slurry of component (b3-1). The average particle
diameter of the resulting component (b3-1) was 4 .mu.m.
A part of the component (b3-1) prepared by the above procedure was
dried and examined for its composition, indicating 26.0 weight %
magnesium, 0.4 weight % aluminum, 4.8 weight % 2-ethylhexoxy group
and 68.0 weight % chlorine. Accordingly, the molar ratio of
magnesium to aluminum (Mg/Al) was 72.2, and the molar ratio of
2-ethylhexoxy group to aluminum (OR/Al) was 0.3.
Preparation of Component (b3-1-a2-172)
A flask having an internal volume of 200 mL purged sufficiently
with nitrogen was charged with purified toluene and component
(b3-1) in an amount of 3 mmol in term of magnesium atom, so as to
adjust the total volume to 85.4 ml. While the sample was kept at
25.degree. C. under stirring, 14.5 mL toluene solution (0.001022
mmol/mL) of the component (a2-172) used in Example 1 was added
dropwise thereto over 20 minutes. After the mixture was stirred for
1 hour, the solids were collected by filtration and washed
sufficiently with toluene, and 50 mL decane was added thereto to
give a decane slurry of component (b3-1-a2-172).
A part of this slurry was collected to analyze its concentration,
indicating 1.29 mg/mL magnesium and 30.9 .mu.g/mL zirconium.
Accordingly, the content of zirconium atom in 1 g of the component
(b3-1-a2-172) was calculated to be 6.23 mg/g.
Polymerization
Polymerization was carried out in the same manner as in Example 10
except that in the Polymerization in Example 10, the component
(b3-1-a2-172) prepared above was used in place of the component
(b1-1-a2-195). As a result, 108.0 g polyethylene was obtained.
Accordingly, the polymerization activity was 308.4 kg/mmol-Zrhr,
and the polymerization activity per g of the component
(b3-1-a2-172) was 21.0 kg/g-cathr, and this polyethylene had a
[.eta.] value of 17.9 dl/g and a bulk density of 0.22
g/cm.sup.3.
Example 19
Preparation of Component (b3-2)
A flask having an internal volume of 200 mL purged sufficiently
with nitrogen was charged with 25 mL component (b3) (25 mmol in
terms of magnesium atom) and 100 mL toluene, and while the
temperature of the solution was kept at -20.degree. C. under
stirring, 26 mmol triethyl aluminum diluted with toluene was added
dropwise thereto over 30 minutes. Thereafter, the temperature of
the solution was increased to 100.degree. C. over 320 minutes, and
the mixture was reacted for 1 hour. While the temperature was kept
at 100.degree. C., 175 mmol triethyl aluminum diluted with toluene
was again added dropwise thereto over 30 minutes, and the mixture
was further reacted under heating for 1 hour. After the reaction
was finished, the solids were collected by filtration and washed
sufficiently with toluene, and 100 mL toluene was added thereto to
form a toluene slurry of component (b3-2). The average particle
diameter of the resulting component (b3-2) was 6 .mu.m.
A part of the component (b3-2) prepared by the above procedure was
dried and examined for its composition, indicating 26.0 weight %
magnesium, 0.4 weight % aluminum, 0.7 weight % 2-ethylhexoxy group
and 19.0 weight % chlorine. Accordingly, the molar ratio of
magnesium to aluminum (Mg/Al) was 72.2, and the molar ratio of
2-ethylhexoxy group to aluminum (OR/Al) was 0.4.
Preparation of Component (b3-2-a2-172)
A flask having an internal volume of 200 mL purged sufficiently
with nitrogen was charged with purified toluene and component
(b3-2) in an amount of 3 mmol in term of magnesium atom, so as to
adjust the total volume to 85.2 mL. While the sample was kept at
25.degree. C. under stirring, 14.8 mL toluene solution (0.001011
mmol/mL) of the component (a2-172) used in Example 1 was added
dropwise thereto over 20 minutes. After the mixture was stirred for
1 hour, the solids were collected by filtration and washed
sufficiently with toluene, and decane was added thereto to give a
decane slurry of component (b3-2-a2-172).
A part of this slurry was collected to analyze its concentration,
indicating 1.05 mg/mL magnesium and 24.7 .mu.g/mL zirconium.
Accordingly, the content of zirconium atom in 1 g of the component
(b3-2-a2-172) was calculated to be 6.12 mg/g.
Polymerization
Polymerization was carried out in the same manner as in Example 10
except that in the Polymerization in Example 10, the component
(b3-2-a2-172) prepared above was used in place of the component
(b1-1-a2-195). As a result, 82.9 g polyethylene was obtained.
Accordingly, the polymerization activity was 236.7 kg/mmol-Zrhr,
and the polymerization activity per g of the component
(b3-2-a2-172) was 15.8 kg/g-cathr, and this polyethylene had a
[.eta.] value of 17.4 dl/g and a bulk density of 0.23
g/cm.sup.3.
Example 20
Preparation of Component (b3-3)
A flask having an internal volume of 400 mL purged sufficiently
with nitrogen was charged with 12.5 mL component (b3) (25 mmol in
terms of magnesium atom) and 250 mL toluene, and while the
temperature of the solution was kept at -20.degree. C. under
stirring, 10.2 mmol triethyl aluminum diluted with toluene was
added dropwise thereto over 30 minutes. Thereafter, the temperature
of the solution was increased to 100.degree. C. over 1160 minutes,
and the mixture was reacted for 1 hour. While the temperature was
kept at 100.degree. C., 87.5 mmol triethyl aluminum diluted with
toluene was again added dropwise thereto over 30 minutes, and the
mixture was further reacted under heating for 1 hour. After the
reaction was finished, the solids were collected by filtration and
washed sufficiently with toluene, and 100 mL toluene was added
thereto to form a toluene slurry of component (b3-3). The average
particle diameter of the resulting component (b3-3) was 5
.mu.m.
A part of the component (b3-3) prepared by the above procedure was
dried and examined for its composition, indicating 24.0 weight %
magnesium, 0.4 weight % aluminum, 0.8 weight % 2-ethylhexoxy group
and 69.0 weight % chlorine. Accordingly, the molar ratio of
magnesium to aluminum (Mg/Al) was 66.6, and the molar ratio of
2-ethylhexoxy group to aluminum (OR/Al) was 0.4.
Preparation of Component (b3-3-a2-172)
A flask having an internal volume of 200 mL purged sufficiently
with nitrogen was charged with purified toluene and component
(b3-3) in an amount of 3 mmol in term of magnesium atom, so as to
adjust the total volume to 85.7 mL. While the sample was kept at
25.degree. C. under stirring, 14.3 mL toluene solution (0.001052
mmol/mL) of the component (a2-172) used in Example 1 was added
dropwise thereto over 20 minutes. After the mixture was stirred for
1 hour, the solids were collected by filtration and washed
sufficiently with toluene, and decane was added thereto to give a
decane slurry of component (b3-3-a2-172).
A part of this slurry was collected to analyze its concentration,
indicating 1.26 mg/mL magnesium and 28.3 .mu.g/mL zirconium.
Accordingly, the content of zirconium atom in 1 g of the component
(b3-3-a2-172) was calculated to be 5.39 mg/g.
Polymerization
Polymerization was carried out in the same manner as in Example 10
except that in the Polymerization in Example 10, the component
(b3-3-a2-172) prepared above was used in place of the component
(b1-1-a2-195). As a result, 99.5 g polyethylene was obtained.
Accordingly, the polymerization activity was 284.3 kg/mmol-Zrhr,
and the polymerization activity per g of the component
(b3-3-a2-172) was 16.8 kg/g-cathr, and this polyethylene had a
[.eta.] value of 22.0 dl/g and a bulk density of 0.22
g/cm.sup.3.
Comparative Example 1
Preparation of Component (b1-8)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with 25 ml component (B1) (25 mmol in
terms of magnesium atom) and 100 ml purified decane, and while the
temperature of the solution was kept at 15.degree. C. under
stirring, 26 mmol triethyl aluminum diluted with purified decane
was added dropwise thereto over 30 minutes. Thereafter, the
temperature of the solution was increased to 80.degree. C. over 2
hours, and the mixture was reacted for 1 hour. After the reaction
was finished, the solids were collected by filtration and washed
sufficiently with toluene, and 100 ml toluene was added thereto to
form a toluene slurry of component (b1-8). The average particle
diameter of the resulting component (b1-8) was 20 .mu.m.
A part of the component (component (b1-8)) prepared by the above
procedure was dried and examined for its composition, indicating
6.5 weight % magnesium, 3.5 weight % aluminum, 78.0 weight %
2-ethylhexoxy group and 18.0 weight % chlorine, and the molar ratio
of magnesium to aluminum (Mg/Al) was 2.0, and the molar ratio of
2-ethylhexoxy group to aluminum (OR/Al) was 4.6.
Preparation of Component (b1-8-a2-1)
A flask having an internal volume of 200 ml purged sufficiently
with nitrogen was charged with component (b1-8) in an amount of 10
mmol in terms of magnesium atom and 100 ml purified toluene, and
while the temperature of the solution was kept at room temperature
under stirring, 50 ml toluene solution (0.001 mmol/ml) of component
(a2-1) below was added dropwise thereto over 20 minutes. After the
mixture was stirred for 1 hour, the solids were collected by
filtration (component (b1-8-a2-1)). A part of the component
(b1-8-a2-1) prepared by the above procedure was dried and examined
for its composition, revealing that the component (a2-1) was hardly
contained (0.004 weight %).
##STR00151##
Comparative Example 2
500 ml purified toluene was introduced into an SUS autoclave having
an internal volume of 1 liter purged sufficiently with nitrogen,
and the liquid phase and gaseous phase were saturated with ethylene
by blowing ethylene. Thereafter, the toluene was heated to
75.degree. C., and the autoclave was charged in an ethylene stream
with 1.9 mmol triisobutyl aluminum and 0.5 ml component (b1) (0.5
mmol in terms of magnesium atom) prepared in the same manner as in
Example 1, and the mixture was reacted for 15 minutes, to prepare a
magnesium-containing carrier component (B) in the system. Then, the
autoclave was charged with component (a2-116), 0.384 mg (0.0005
mmol in terms of zirconium atom), and polymerization was carried
out for 15 minutes at an ethylene pressure of 0.8 MPaG. During the
polymerization, the system was kept at 75.degree. C. and at an
ethylene pressure of 0.8 MPaG. After the polymerization was
finished, the reaction product was introduced into a large amount
of methanol to precipitate the whole polymer, and after
hydrochloric acid was added, the polymer was collected with a glass
filter. The resulting polymer was dried under vacuum for 10 hours
to give 33.25 g polyethylene. The [.eta.] value of this
polyethylene was 15.8 dl/g.
The polymerization activity per molecule of the component (a2-116)
was as high as 266,000 g/mmol-Zrhr, but the activity of 1 g
starting material used in preparation of the carrier component (B)
was as very low as 0.2 kg/g-cathr, and the bulk density was also as
low as 0.09 g/cm.sup.3.
The calculated molar ratio of magnesium to aluminum (Mg/Al) in the
system was 0.26, and the calculated molar ratio of 2-ethylhexoxy
group to aluminum (OR/Al) was 0.79. Separately, the carrier
component (B) was prepared in the same method as described above,
and its measured particle diameter was 1 .mu.m or less.
INDUSTRIAL APPLICABILITY
The present invention is industrially useful because an olefin
polymer excellent in powdery properties can be obtained by an
extremely high polymerization activity even without combination
with an expensive organoaluminum oxy compound or organoboron
compound.
* * * * *